TWI807010B - Photosensitive resin composition, photo-spacer and liquid crystal display device - Google Patents

Abstract

本發明之課題係提供一種感光性樹脂組成物、與使用其之光間隔物及液晶顯示裝置之製造方法，該感光性樹脂組成物在使用作為間隔物時，係抑制了塑性變形之高恢復率的光間隔物，同時極力抑制削減設置於對向的基板之液晶配向膜；本發明之宗旨係在於一種感光性樹脂組成物、使用其而形成光間隔物、使用其之液晶顯示裝置，該感光性樹脂組成物係含有鹼可溶性樹脂、光聚合起始劑及聚合性化合物之感光性樹脂組成物，其中在該樹脂組成物之固體成分中求出之胺基甲酸酯當量為1000~50000g/mol，且乙烯性不飽和基當量為100~155g/mol。 The subject of the present invention is to provide a photosensitive resin composition, a photo-spacer using it, and a method for manufacturing a liquid crystal display device. When the photosensitive resin composition is used as a spacer, it is a photo-spacer with a high recovery rate that suppresses plastic deformation, and at the same time suppresses as much as possible the reduction of the liquid crystal alignment film disposed on the opposite substrate. A photosensitive resin composition of an agent and a polymerizable compound, wherein the urethane equivalent obtained in the solid content of the resin composition is 1,000 to 50,000 g/mol, and the ethylenically unsaturated group equivalent is 100 to 155 g/mol.

Description

感光性樹脂組成物、光間隔物及液晶顯示裝置 Photosensitive resin composition, photo-spacer and liquid crystal display device

本發明係關於一種感光性樹脂組成物、使用其之光間隔物及液晶顯示裝置。 The present invention relates to a photosensitive resin composition, a photo-spacer using it and a liquid crystal display device.

液晶顯示裝置係活用輕量、薄型、低耗電等特性，而可使用於筆記型電腦、攜帶型數據終端、智慧型手機、數位相機及桌上型顯示器等各種用途。 Liquid crystal display devices are lightweight, thin, and low power consumption, and can be used in various applications such as notebook computers, portable data terminals, smart phones, digital cameras, and desktop displays.

液晶顯示裝置具備：在濾光片基板與TFT(Thin Film Transistor)陣列基板之間，藉由因電場之配向而控制在畫素單位下的光之穿透，因而可顯示影像之液晶層；此等基板之間隔(液晶間隙)保持均勻，係左右畫質之重要的要素之一。 The liquid crystal display device is equipped with: between the filter substrate and the TFT (Thin Film Transistor) array substrate, the liquid crystal layer that can display images by controlling the penetration of light in the pixel unit due to the alignment of the electric field; the gap between these substrates (liquid crystal gap) is kept uniform, which is one of the important factors that affect the image quality.

作為均勻保持液晶間隙之手段，以往進行：在基板上的非顯示區域形成具有對應於液晶間隙的高度之間隔物。該間隔物例如在基板上均勻塗布感放射線性樹脂，進行圖案曝光，此後藉由鹼顯影的光蝕刻法而形成(使用感放射線性樹脂而形成之間隔物亦稱為光間隔物)。 As a means for uniformly maintaining the liquid crystal gap, conventionally, spacers having a height corresponding to the liquid crystal gap are formed in a non-display region on a substrate. The spacer is, for example, uniformly coated with a radiation-sensitive resin on the substrate, subjected to pattern exposure, and then formed by a photolithography method of alkali development (a spacer formed using a radiation-sensitive resin is also called a photo-spacer).

然而，製造液晶顯示面板時，在使濾光片與TFT陣列基板壓接時，樹脂製的間隔物因壓接時的壓力 而易於塑性變形，又，另一方面，壓接時的壓力使液晶面板面內不均勻，因此間隔物的高度不一致，其結果為具有易於在畫素中發生顯示不均之課題。 However, when manufacturing a liquid crystal display panel, when the filter is bonded to the TFT array substrate, the resin spacer is likely to be plastically deformed by the pressure during the pressure bonding. On the other hand, the pressure during the pressure bonding makes the surface of the liquid crystal panel non-uniform, so the height of the spacer is not uniform. As a result, there is a problem that display unevenness is likely to occur in the pixel.

作為抑制間隔物之塑性變形之技術，已提案一種間隔物用感光性樹脂組成物(例如參照專利文獻1)等，該間隔物用感光性樹脂組成物係以鹼可溶性樹脂、光聚合起始劑、及聚合性單體作為主成分之間隔物用感光性樹脂組成物，其特徵為此等感光性樹脂組成物全體的丙烯酸當量為200以下。 As a technique for suppressing plastic deformation of spacers, a photosensitive resin composition for spacers has been proposed (for example, refer to Patent Document 1). The photosensitive resin composition for spacers is a photosensitive resin composition for spacers containing an alkali-soluble resin, a photopolymerization initiator, and a polymerizable monomer as main components. It is characterized in that the acrylic acid equivalent of the entire photosensitive resin composition is 200 or less.

又，近年來，為了提升產率，已提案使用不需要摩擦的光配向用液晶配向劑之技術(例如參照專利文獻2)等。 Moreover, in recent years, in order to improve productivity, the technique which uses the liquid crystal alignment agent for photo-alignment which does not require rubbing has been proposed (for example, refer patent document 2).

又，亦已知在樹脂組成物摻合異氰酸酯，在樹脂組成物之熱硬化時形成胺基甲酸酯鍵結之技術(例如參照專利文獻3)，然而，由於熱硬化條件之選擇的限制，無法充分完成反應，因此無法得到最佳特性。 In addition, there is also known a technique of mixing isocyanate into a resin composition to form a urethane bond during thermosetting of the resin composition (for example, refer to Patent Document 3). However, due to limitations in the selection of thermosetting conditions, the reaction cannot be fully completed, and thus optimum characteristics cannot be obtained.

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Document]

[專利文獻1]日本特開2005-292269號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 2005-292269

[專利文獻2]日本特開2017-203980號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2017-203980

[專利文獻3]日本特開2006-276159號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2006-276159

在專利文獻1記載之發明中，已顯示減少樹 脂組成物中的乙烯性不飽和基當量作為縮小彈性變形率之手段。若減少樹脂組成物中的乙烯性不飽和基當量，則間隔物變硬。另一方面，為了控制液晶之配向方向而在基板上設置液晶配向膜。然而，液晶配向膜有機械強度弱，容易發生刮傷之問題，近年來代替摩擦配向劑使用之光配向用液晶配向劑，該傾向尤其顯著。 In the invention described in Patent Document 1, reduction of the ethylenically unsaturated group equivalent in the resin composition is shown as a means for reducing the elastic deformation rate. When the ethylenically unsaturated group equivalent in the resin composition is reduced, the spacer becomes hard. On the other hand, in order to control the alignment direction of the liquid crystal, a liquid crystal alignment film is provided on the substrate. However, the liquid crystal alignment film has the problem of weak mechanical strength and prone to scratches. In recent years, the liquid crystal alignment agent for photo-alignment used instead of the rubbing alignment agent has a significant tendency.

亦即，在縮小乙烯性不飽和基當量的前述專利文獻1之技術中，有變硬的間隔物會削減設置於對向的基板之配向膜的權衡關係。 That is, in the technique of the aforementioned Patent Document 1 in which the ethylenically unsaturated group equivalent is reduced, there is a trade-off relationship in which the hardened spacer reduces the alignment film provided on the opposing substrate.

因此，本發明之目的係提供一種感光性樹脂組成物、與使用其之光間隔物及液晶顯示裝置之製造方法，該感光性樹脂組成物係使用作為間隔物時，係抑制了塑性變形之高恢復率的光間隔物，同時極力抑制削減設置於對向的基板之液晶配向膜。 Therefore, the object of the present invention is to provide a photosensitive resin composition, a photo-spacer using it, and a method for manufacturing a liquid crystal display device. When the photosensitive resin composition is used as a spacer, it is a photo-spacer with a high recovery rate that suppresses plastic deformation, and at the same time suppresses as much as possible the reduction of the liquid crystal alignment film disposed on the opposite substrate.

為了解決上述課題，本發明主要具有以下構成。 In order to solve the above-mentioned problems, the present invention mainly has the following configurations.

亦即，一種感光性樹脂組成物，其係含有鹼可溶性樹脂、光聚合起始劑及聚合性化合物之感光性樹脂組成物，其中在該樹脂組成物之固體成分中求出之胺基甲酸酯當量為1000~50000g/mol，且乙烯性不飽和基當量為100~155g/mol。 That is, a photosensitive resin composition, which is a photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator, and a polymerizable compound, wherein the urethane equivalent obtained in the solid content of the resin composition is 1,000 to 50,000 g/mol, and the ethylenically unsaturated group equivalent is 100 to 155 g/mol.

又，本發明之其他態樣係使用該感光性樹脂組成物而形成之光間隔物、及具備該光間隔物之液晶顯示裝置。 Moreover, another aspect of this invention is the liquid crystal display device provided with the photo-spacer formed using this photosensitive resin composition, and this photo-spacer.

根據本發明，可作成使用作為光間隔物時，抑制了塑性變形之高恢復率的光間隔物，又，可極力抑制削減設置於對向的基板之液晶配向膜的現象。 According to the present invention, when used as a photo-spacer, a photo-spacer with a high recovery rate that suppresses plastic deformation can be produced, and the phenomenon of reducing the liquid crystal alignment film provided on the opposing substrate can be suppressed as much as possible.

Ha‧‧‧光間隔物之總變形量[μm] Ha‧‧‧Total deformation of photo-spacer [μm]

Hb‧‧‧光間隔物之塑性變形量[μm] Hb‧‧‧Plastic deformation of photo-spacer [μm]

圖1係表示光間隔物之彈性特性的負重-變形量遲滯曲線(hysteresis curve)之一例。 FIG. 1 is an example of a load-deformation hysteresis curve showing elastic properties of a photo-spacer.

本發明之感光性樹脂組成物至少含有鹼可溶性樹脂、光聚合起始劑及聚合性化合物。藉由含有光聚合起始劑及聚合性化合物，可藉由光聚合而使曝光部光硬化，不溶於鹼顯影液，又，藉由含有鹼可溶性樹脂，可透過藉由鹼顯影液的顯影步驟而去除未曝光部，因此可應用於所謂的光蝕刻技術，可藉由曝光及顯影而形成所欲的圖案。 The photosensitive resin composition of the present invention contains at least an alkali-soluble resin, a photopolymerization initiator, and a polymerizable compound. By containing a photopolymerization initiator and a polymerizable compound, the exposed part can be photohardened by photopolymerization and insoluble in an alkali developer, and by containing an alkali-soluble resin, the unexposed part can be removed through the development step by an alkali developer, so it can be applied to the so-called photoetching technology, and a desired pattern can be formed by exposure and development.

在本發明之感光性樹脂組成物中，在該樹脂組成物之固體成分中求出之胺基甲酸酯當量為1000~50000g/mol，且乙烯性不飽和基當量為100~155g/mol。 In the photosensitive resin composition of the present invention, the urethane equivalent obtained in the solid content of the resin composition is 1000-50000 g/mol, and the ethylenically unsaturated group equivalent is 100-155 g/mol.

在此所謂的固體成分，係指除了感光性樹脂組成物所包含之溶劑以外的成分。無法分離為各成分的樹脂組成物之情形的固體成分，可藉由在130℃下加熱1小時而使溶劑飛散，測定殘餘物之質量而求出。 The term "solid content" here refers to components other than the solvent contained in the photosensitive resin composition. In the case of a resin composition that cannot be separated into individual components, the solid content can be obtained by heating at 130° C. for 1 hour to scatter the solvent, and measuring the mass of the residue.

本發明之感光性樹脂組成物係由在其固體成分中具有規定的乙烯性不飽和基當量可知，含有包含乙 烯性不飽和基之化合物。 The photosensitive resin composition of the present invention contains a compound containing an ethylenically unsaturated group as known to have a predetermined ethylenically unsaturated group equivalent in its solid content.

在此，乙烯性不飽和基當量係指為了賦予1莫耳的乙烯性不飽和基所需要的化合物之公克數，該值愈小，表示每單位質量所包含之乙烯性不飽和基的量愈多。在不具有乙烯性不飽和基的化合物中，乙烯性不飽和基當量為無限大。又，在本發明之感光性樹脂組成物之固體成分中可含有多個化合物時，例如固體成分為三成分系統，將其一個成分的A成分之乙烯性不飽和基當量作為Ea，將其固體成分中的質量分率作為Wa，同樣地將B成分之乙烯性不飽和基當量作為Eb，將其固體成分中的質量分率作為Wb，將C成分之乙烯性不飽和基當量作為Ec，將其固體成分中的質量分率作為Wc時，作為固體成分之乙烯性不飽和基當量(Etotal)可使用下式而求出。此外，在此，由於該例之系統為三成分系統，因此Wa+Wb+Wc=1。此外，3成分系統以外之情形亦可同樣地求出包含多個成分之情形的固體成分之乙烯性不飽和基當量。 Here, the ethylenically unsaturated group equivalent means the number of grams of the compound required to impart 1 mole of ethylenically unsaturated groups, and the smaller the value, the greater the amount of ethylenically unsaturated groups contained per unit mass. In a compound not having an ethylenically unsaturated group, the ethylenically unsaturated group equivalent is infinite. In addition, when a plurality of compounds may be contained in the solid content of the photosensitive resin composition of the present invention, for example, the solid content is a three-component system, and the ethylenically unsaturated group equivalent of the A component of one component is Ea, and the mass fraction in the solid content is Wa; similarly, when the ethylenically unsaturated group equivalent of the B component is Eb, the mass fraction in the solid content is Wb, the ethylenically unsaturated group equivalent of the C component is Ec, and the mass fraction in the solid content is Wc, The ethylenically unsaturated group equivalent (Etotal) as a solid content can be calculated|required using the following formula. In addition, here, since the system of this example is a three-component system, Wa+Wb+Wc=1. In addition, the ethylenic unsaturated group equivalent of the solid content in the case of including a plurality of components can also be calculated|required similarly in the case other than a 3-component system.

(1/Etotal)=(1/Ea×Wa+1/Eb×Wb+1/Ec×Wc)。 (1/Etotal)=(1/Ea×Wa+1/Eb×Wb+1/Ec×Wc).

然而，當難以求出構成固體成分之成分個別的乙烯性不飽和基當量時，可利用求出固體成分之質量、或藉由光譜學方法、化學方法而求出該固體成分所包含之乙烯性不飽和基的總量，而求出固體成分之乙烯性不飽和基當量。 However, when it is difficult to obtain the individual ethylenically unsaturated group equivalents of the components constituting the solid components, the ethylenically unsaturated group equivalents of the solid components can be obtained by obtaining the mass of the solid components, or obtaining the total amount of ethylenically unsaturated groups contained in the solid components by spectroscopic methods or chemical methods.

本發明之感光性樹脂組成物之固體成分中求 出之乙烯性不飽和基當量為100~155g/mol。當大於155g/mol時，成為作成間隔物時之塑性變形降低者。另一方面，當小於100g/mol時，作成間隔物時之體積收縮變得明顯小於液晶之體積收縮，其結果為在低溫保存液晶面板時，容易發生液晶之發泡而成為顯示品質低劣者，又，有在顯影時發生欠缺間隔物的現象之情形。 The ethylenically unsaturated group equivalent obtained in the solid content of the photosensitive resin composition of the present invention is 100 to 155 g/mol. When it exceeds 155 g/mol, the plastic deformation when used as a spacer is reduced. On the other hand, when it is less than 100 g/mol, the volume shrinkage when forming spacers becomes significantly smaller than the volume shrinkage of liquid crystals. As a result, when storing liquid crystal panels at low temperatures, foaming of liquid crystals tends to occur, resulting in poor display quality, and spacers may be missing during development.

作為降低樹脂組成物之固體成分中求出之乙烯性不飽和基當量之方法，可列舉：使用乙烯性不飽和基當量低的聚合性化合物、或在鹼可溶性樹脂導入乙烯性不飽和基之方法；使用密合改良劑、界面活性劑作為導入了乙烯性不飽和基之添加劑之方法。在調整為本發明所規定的範圍時，只要調整各成分之乙烯性不飽和基當量與其質量分率即可，係屬自明之理。 As a method of reducing the ethylenically unsaturated group equivalent obtained in the solid content of the resin composition, there may be mentioned: a method of using a polymerizable compound having a low ethylenically unsaturated group equivalent, a method of introducing an ethylenically unsaturated group into an alkali-soluble resin, and a method of using an adhesion improving agent or a surfactant as an additive for introducing an ethylenically unsaturated group. When adjusting to the range specified in the present invention, it is self-evident that only the ethylenically unsaturated group equivalent and its mass fraction of each component can be adjusted.

本發明之感光性樹脂組成物係由在其固體成分中具有規定的胺基甲酸酯當量可知，含有包含胺基甲酸酯鍵結之化合物。 The photosensitive resin composition of the present invention contains a compound including a urethane bond as can be seen from having a predetermined urethane equivalent in its solid content.

在此，胺基甲酸酯當量係指為了賦予1莫耳的胺基甲酸酯鍵結所需要的化合物之公克數，該值愈小，表示每單位質量所包含之胺基甲酸酯鍵結的量愈多。在不具有胺基甲酸酯鍵結的化合物中，胺基甲酸酯當量為無限大。又，在本發明之感光性樹脂組成物之固體成分中可含有多個化合物時，該情形的求出胺基甲酸酯當量之方法，係可藉由與前述乙烯性不飽和基當量同樣的觀念而求出。此外，關於難以求出構成固體成分之成分個別的胺基甲酸酯當量之情形的求出方法，亦與上 述同樣地理解。順帶一提，胺基甲酸酯鍵結由於在紅外線光譜分析中在1550cm^-1附近具有波峰，因此可利用檢量線法而求出胺基甲酸酯鍵結之量。 Here, the urethane equivalent means the number of grams of the compound required to impart 1 mole of urethane linkages, and the smaller the value, the greater the amount of urethane linkages contained per unit mass. In compounds having no urethane linkages, the urethane equivalent weight is infinite. Also, when a plurality of compounds can be contained in the solid content of the photosensitive resin composition of the present invention, the method of obtaining the urethane equivalent in this case can be obtained from the same concept as the above-mentioned ethylenically unsaturated group equivalent. In addition, about the calculation method in the case where it is difficult to obtain the individual urethane equivalents of the components constituting the solid content, it can be understood in the same manner as above. Incidentally, since the urethane bond has a peak around 1550 cm ⁻¹ in the infrared spectroscopic analysis, the amount of the urethane bond can be obtained by the calibration curve method.

本發明之感光性樹脂組成物之固體成分中求出之胺基甲酸酯當量為1000~50000g/mol。當胺基甲酸酯當量大於50000g/mol時，對於設置於對向的基板之液晶配向膜的損傷抑制並不充分，又，當小於1000時，在作成間隔物時，顯影性降低，難以調整間隔物之形狀、高度。 The urethane equivalent obtained in the solid content of the photosensitive resin composition of the present invention is 1000-50000 g/mol. When the urethane equivalent is greater than 50,000 g/mol, the damage suppression of the liquid crystal alignment film disposed on the opposite substrate is not sufficient, and when it is less than 1000, when the spacer is made, the developability is reduced, and it is difficult to adjust the shape and height of the spacer.

在本發明之感光性樹脂組成物中，作為前述包含胺基甲酸酯鍵結之化合物，藉由使用分子量3000以下者，顯影寬容度容易變廣而較佳。 In the photosensitive resin composition of the present invention, it is preferable to use a compound having a molecular weight of 3,000 or less as the compound containing a urethane bond, since the development latitude tends to widen.

又，在本發明之感光性樹脂組成物中，作為胺基甲酸酯當量除以乙烯性不飽和基當量之值，係以5~200為佳，藉由設為該範圍，易於兼顧彈性恢復率與配向膜之耐損傷性。 In addition, in the photosensitive resin composition of the present invention, the value of dividing the urethane equivalent by the ethylenically unsaturated group equivalent is preferably 5 to 200. By setting it in this range, it is easy to balance the elastic recovery rate and the damage resistance of the alignment film.

樹脂組成物之固體成分中求出之胺基甲酸酯當量之調整，可藉由所使用之具有胺基甲酸酯鍵結之化合物的胺基甲酸酯當量與固體成分中的質量分率而推測，而胺基甲酸酯鍵結可導入鹼可溶性樹脂之主鏈或側鏈，亦可在製備聚合性化合物時藉由使異氰酸酯化合物與丙烯酸單體反應而導入聚合性化合物中。又，作為其他方法，亦可使用如後述之含有胺基甲酸酯鍵結之矽烷偶合劑。 The adjustment of the urethane equivalent obtained in the solid content of the resin composition can be estimated from the urethane equivalent of the compound having the urethane bond used and the mass fraction in the solid content. The urethane bond can be introduced into the main chain or side chain of the alkali-soluble resin, and can also be introduced into the polymerizable compound by reacting the isocyanate compound and the acrylic monomer when preparing the polymeric compound. In addition, as another method, a urethane bond-containing silane coupling agent as described later can also be used.

本發明中的聚合性化合物，係因一同使用之 光聚合起始劑的作用而發生聚合反應之化合物，作為典型的光聚合性之官能基，可列舉乙烯性不飽和基。又，本發明中的聚合性化合物，其分子量為3000以下。作為本發明所使用之聚合性化合物，例如可列舉：單官能或多官能之單體、寡聚物等。從在一分子中尤其提高交聯密度且提升彈性恢復率來看，本發明所使用之聚合性化合物係以多官能單體為較佳。尤其從易於提高加工為間隔物時之彈性恢復率來看，係以使用在1分子中具有6個以上的乙烯性不飽和基者為較佳。進一步較佳係以使用在1分子中具有6個以上25個以下的乙烯性不飽和基者為較佳。作為多官能之聚合性單體，例如可列舉：三丙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚A二環氧丙基醚二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三丙烯酸二甲醇縮甲醛、季戊四醇四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、9,9-雙[4-(3-丙烯醯氧基-2-羥丙氧基)苯基]茀、9,9-雙[3-甲基-4-(3-丙烯醯氧基-2-羥丙氧基)苯基]茀、9,9-雙[3-氯-4-(3-丙烯醯氧基-2-羥丙氧基)苯基]茀、雙苯氧基乙醇茀二丙烯酸酯、雙苯氧基乙醇茀二甲基丙烯酸酯、三季戊四醇八丙烯酸酯、二季戊四醇五丙烯酸酯與琥珀酸酐之反應物等。作為聚合性化合物，可使用1種，亦可使用2種以上。 The polymerizable compound in the present invention is a compound that undergoes a polymerization reaction due to the action of the photopolymerization initiator used together, and typical photopolymerizable functional groups include ethylenically unsaturated groups. Moreover, the polymerizable compound in this invention has a molecular weight of 3000 or less. Examples of the polymerizable compound used in the present invention include monofunctional or polyfunctional monomers, oligomers, and the like. From the point of view of increasing the crosslinking density and improving the elastic recovery rate in one molecule, the polymeric compound used in the present invention is preferably a multifunctional monomer. In particular, it is preferable to use one having six or more ethylenically unsaturated groups in one molecule from the viewpoint of easiness of improving the elastic recovery rate when processed into a spacer. More preferably, it is more preferable to use what has 6 or more and 25 or less ethylenically unsaturated groups in 1 molecule. Examples of polyfunctional polymerizable monomers include tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylic acid dimethanol formal, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol Tetrol octa(meth)acrylate, tripentaerythritol octa(meth)acrylate, 9,9-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]oxene, 9,9-bis[3-methyl-4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]oxene, 9,9-bis[3-chloro-4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]oxene, bisphenoxyethanol Diacrylate, bisphenoxyethanol stilbene dimethacrylate, tripentaerythritol octaacrylate, dipentaerythritol pentaacrylate and succinic anhydride reactant, etc. As the polymerizable compound, one type may be used, or two or more types may be used.

又，聚合性化合物係以其分子量為700~ 3000之範圍，且含有胺基甲酸酯鍵結為較佳。作為這樣的化合物之具體例，可列舉：六亞甲基二異氰酸酯之季戊四醇四丙烯酸酯加成物(765(數字表示分子量，以下在本段落中皆相同))、六亞甲基二異氰酸酯之二季戊四醇五丙烯酸酯加成物(1217)、六亞甲基二異氰酸酯之三季戊四醇八丙烯酸酯加成物(1670)、六亞甲基二異氰酸酯脲二酮體之季戊四醇四丙烯酸酯加成物(905)、六亞甲基二異氰酸酯脲二酮體之二季戊四醇五丙烯酸酯加成物(1357)、六亞甲基二異氰酸酯脲二酮體之三季戊四醇八丙烯酸酯加成物(1810)、六亞甲基二異氰酸酯異三聚氰酸酯體之丙烯酸加成物(721)、六亞甲基二異氰酸酯異三聚氰酸酯體之季戊四醇四丙烯酸酯加成物(1399)、六亞甲基二異氰酸酯異三聚氰酸酯體之二季戊四醇五丙烯酸酯加成物(2078)、六亞甲基二異氰酸酯異三聚氰酸酯體之三季戊四醇八丙烯酸酯加成物(2757)、六亞甲基二異氰酸酯異三聚氰酸酯體之二季戊四醇三丙烯酸酯‧環氧烷轉化物加成物(2927)、伸苯基二異氰酸酯之季戊四醇四丙烯酸酯加成物(757)、伸苯基二異氰酸酯之二季戊四醇五丙烯酸酯加成物(1209)、伸苯基二異氰酸酯之三季戊四醇八丙烯酸酯加成物(1662)、甲伸苯基二異氰酸酯之季戊四醇四丙烯酸酯加成物(771)、甲伸苯基二異氰酸酯之二季戊四醇五丙烯酸酯加成物(1223)、甲伸苯基二異氰酸酯之三季戊四醇八丙烯酸酯加成物(1676)、異佛酮二異氰酸酯之季戊四醇四丙烯酸酯加成物(819)、異佛酮二異氰酸酯之二季戊四醇五丙烯酸酯加成物(1271)、 異佛酮二異氰酸酯之三季戊四醇八丙烯酸酯加成物(1724)、二環己基甲烷二異氰酸酯之季戊四醇四丙烯酸酯加成物(859)、二環己基甲烷二異氰酸酯之二季戊四醇五丙烯酸酯加成物(1311)、二環己基甲烷二異氰酸酯之三季戊四醇八丙烯酸酯加成物(1764)、二苯基甲烷二異氰酸酯之季戊四醇四丙烯酸酯加成物(847)、二苯基甲烷二異氰酸酯之二季戊四醇五丙烯酸酯加成物(1299)、二苯基甲烷二異氰酸酯之三季戊四醇八丙烯酸酯加成物(1752)、降莰烯二異氰酸酯之季戊四醇四丙烯酸酯加'成物(801)、降莰烯二異氰酸酯之二季戊四醇五丙烯酸酯加成物(1253)、降莰烯二異氰酸酯之三季戊四醇八丙烯酸酯加成物(1706)等。若使用該聚合性化合物，則難以產生胺基甲酸酯顯影殘渣。由於配向膜之耐損傷性，聚合性化合物係以其分子量為1000~3000之範圍，且含有胺基甲酸酯鍵結為進一步較佳。在此，欲使異氰酸酯基與羧基反應而在聚合性化合物中導入胺基甲酸酯鍵結時，減少殘存的異氰酸酯基因可最大限度地發揮彈性恢復率而較佳。再者，從樹脂組成物之安定性的層面來看，聚合性化合物中異氰酸酯當量亦以50000g/mol以上為較佳。作為上限，並未特別限制，係以異氰酸酯當量而言為無限大、亦即無法偵測出異氰酸酯基為最佳，而以500000g/mol以下之程度為符合實際者。此外，異氰酸酯基當量可藉由實施例之項目所記載之方法而求出。當難以測定時，亦可進行紅外線光譜測定而基於2260cm^-1之波峰，利用檢量線法而算出。 In addition, the polymeric compound preferably has a molecular weight in the range of 700 to 3000 and contains urethane linkages. Specific examples of such compounds include pentaerythritol tetraacrylate adduct of hexamethylene diisocyanate (765 (numbers indicate molecular weight, the same applies hereinafter)), dipentaerythritol pentaacrylate adduct of hexamethylene diisocyanate (1217), tripentaerythritol octaacrylate adduct of hexamethylene diisocyanate (1670), and pentaerythritol tetraacrylate adduct of hexamethylene diisocyanate uretione (905), dipentaerythritol pentaacrylate adduct of hexamethylene diisocyanate uretdione (1357), tripentaerythritol octaacrylate adduct of hexamethylene diisocyanate uretdione (1810), acrylic acid adduct of hexamethylene diisocyanate isocyanurate (721), pentaerythritol tetraacrylate adduct of hexamethylene diisocyanate isocyanurate (1399), Dipentaerythritol pentaacrylate adduct of methylene diisocyanate isocyanurate (2078), tripentaerythritol octaacrylate adduct of hexamethylene diisocyanate isocyanurate (2757), dipentaerythritol triacrylate‧alkylene oxide conversion adduct of hexamethylene diisocyanate isocyanurate (2927), pentaerythritol tetraacrylate adduct of phenylene diisocyanate (757), Dipentaerythritol pentaacrylate adduct of phenylene diisocyanate (1209), tripentaerythritol octaacrylate adduct of phenylene diisocyanate (1662), pentaerythritol tetraacrylate adduct of toluene diisocyanate (771), dipentaerythritol pentaacrylate adduct of toluene diisocyanate (1223), tripentaerythritol octaacrylate adduct of toluene diisocyanate (167 6) Pentaerythritol tetraacrylate adduct of isophorone diisocyanate (819), dipentaerythritol pentaacrylate adduct of isophorone diisocyanate (1271), tripentaerythritol octaacrylate adduct of isophorone diisocyanate (1724), pentaerythritol tetraacrylate adduct of dicyclohexylmethane diisocyanate (859), dipentaerythritol of dicyclohexylmethane diisocyanate Pentaacrylate adduct (1311), tripentaerythritol octaacrylate adduct of dicyclohexylmethane diisocyanate (1764), diphenylmethane diisocyanate pentaerythritol tetraacrylate adduct (847), diphenylmethane diisocyanate dipentaerythritol pentaacrylate adduct (1299), diphenylmethane diisocyanate tripentaerythritol octaacrylate adduct (1752), Pentaerythritol tetraacrylate adduct of camphene diisocyanate (801), noramphene diisocyanate dipentaerythritol pentaacrylate adduct (1253), norcamphene diisocyanate tripentaerythritol octaacrylate adduct (1706), etc. When this polymerizable compound is used, urethane image development residues are less likely to be generated. Due to the damage resistance of the alignment film, it is further preferred that the polymeric compound has a molecular weight in the range of 1000-3000 and contains urethane linkages. Here, when introducing a urethane bond into a polymerizable compound by reacting an isocyanate group with a carboxyl group, it is preferable to reduce the number of remaining isocyanate genes so as to maximize the elastic recovery rate. Furthermore, from the viewpoint of the stability of the resin composition, the equivalent weight of isocyanate in the polymerizable compound is preferably 50000 g/mol or more. The upper limit is not particularly limited, and it is best that the isocyanate equivalent is infinite, that is, no isocyanate group can be detected, and it is practical to be below 500,000 g/mol. In addition, the isocyanate group equivalent can be calculated|required by the method described in the item of an Example. When it is difficult to measure, it can also be calculated by the calibration curve method based on the peak at 2260 cm ^-1 by performing infrared spectroscopic measurement.

作為在本發明中所使用之聚合性化合物，係以下述通式(1)或下述通式(2)所示之化合物為較佳。 As the polymerizable compound used in the present invention, a compound represented by the following general formula (1) or the following general formula (2) is preferable.

在此，通式(1)與通式(2)中，R¹~R³、R⁷~R⁸分別獨立表示可具有取代基的骨架碳數1~20之伸烷基、可具有取代基的骨架碳數1~20之環氧烷基、或可具有取代基的骨架碳原子數7~30之伸芳基。在此，取代基係選自包含碳數3以下之烷氧基、碳數4以下之羰基、碳數4以下之酯基、碳數4以下之醯胺基、乙烯基、丙烯酸基、甲基丙烯酸基、胺基、羥基、羧基、硝基、鹵素基、異氰酸酯基及腈基之群組。R⁴~R⁶、R⁹~R¹⁰分別獨立表示通式(3)所示之基。 Here, in the general formula (1) and the general formula (2), R ¹ ~ R ³ , R ⁷ ~ R ⁸ independently represent an alkylene group with a skeleton carbon number of 1 to 20 that may have a substituent, an epoxyalkylene group with a skeleton carbon number of 1 to 20 that may have a substituent, or an arylylene group with a skeleton carbon number of 7 to 30 that may have a substituent. Here, the substituent is selected from a group comprising an alkoxy group with 3 or less carbons, a carbonyl group with 4 or less carbons, an ester group with 4 or less carbons, an amide group with 4 or less carbons, a vinyl group, an acrylic group, a methacrylic group, an amino group, a hydroxyl group, a carboxyl group, a nitro group, a halogen group, an isocyanate group, and a nitrile group. R ⁴ ~R ⁶ , R ⁹ ~R ¹⁰ each independently represent a group represented by the general formula (3).

在此，n為1~7之整數，R¹¹~R¹³分別表示通式(4)所示之一價的基。從易於提高彈性恢復率來看，較佳為n為2~7。 Here, n is an integer of 1 to 7, and R ¹¹ to R ¹³ each represent a valent group represented by the general formula (4). From the viewpoint of easiness of improving the elastic recovery rate, n is preferably 2-7.

在此，R¹⁴表示氫原子、或甲基。 Here, R ¹⁴ represents a hydrogen atom or a methyl group.

若使用通式(1)或通式(2)所示之化合物作為聚合性化合物，則由於此等在化學結構中具有難以彎曲的環結構，因此當作成光間隔物時，胺基甲酸酯與乙烯性不飽和基不會不均勻地存在，會均勻分布而易於發揮性能。尤其通式(1)所示之聚合性化合物因為在1分子中包含3個胺基甲酸酯鍵結，因此易於最大限度地發揮柔軟性能。 If the compound represented by the general formula (1) or general formula (2) is used as a polymerizable compound, since these have a difficult-to-bend ring structure in the chemical structure, when used as a photo-spacer, the urethane and ethylenically unsaturated groups will not exist unevenly, and will be uniformly distributed to facilitate performance. In particular, since the polymeric compound represented by the general formula (1) contains three urethane bonds in one molecule, it is easy to maximize the flexibility.

本發明所使用之鹼可溶性樹脂，係指在結構單元具有羧基、羥基等酸性基而溶解於鹼顯影液者，以其分子量而言，大於3000者。再者，為了提高作為光間隔物之彈性恢復率，係以在側鏈包含乙烯性不飽和基為較佳。可為了配向膜之耐損傷性而包含胺基甲酸酯鍵結。 Alkali-soluble resins used in the present invention refer to those having acidic groups such as carboxyl groups and hydroxyl groups in the structural units, which are soluble in alkaline developer, and whose molecular weight is greater than 3000. Furthermore, in order to increase the elastic recovery rate as a photo-spacer, it is preferable to include an ethylenically unsaturated group in the side chain. Urethane linkages may be included for damage resistance of the alignment film.

作為乙烯性不飽和基，例如可列舉：乙烯基、 烯丙基、丙烯酸基、甲基丙烯酸基等。作為將乙烯性不飽和基導入鹼可溶性樹脂之方法，可列舉：在成為具有羧基、羥基之基的樹脂進行加成反應而導入具有環氧基之乙烯性不飽和化合物、丙烯醯氯、甲基丙烯醯氯等之方法。作為導入胺基甲酸酯鍵結之方法，可列舉：利用異氰酸酯而使胺基甲酸酯基加成之方法等。又，當利用異氰酸酯而使具有乙烯性不飽和基之化合物加成時，可同時導入胺基甲酸酯與乙烯性不飽和基。 As an ethylenically unsaturated group, a vinyl group, an allyl group, an acryl group, a methacryl group etc. are mentioned, for example. As a method of introducing an ethylenically unsaturated group into an alkali-soluble resin, a method of introducing an ethylenically unsaturated compound having an epoxy group, acryl chloride, methacryl chloride, etc. by adding reaction to a resin having a carboxyl group or a hydroxyl group can be mentioned. As a method of introducing a urethane bond, the method of adding a urethane group using isocyanate, etc. are mentioned. Moreover, when the compound which has an ethylenically unsaturated group is added using isocyanate, a urethane and ethylenically unsaturated group can be introduced simultaneously.

作為在側鏈具有乙烯性不飽和基之鹼可溶性樹脂，例如可列舉：Daicel-Allnex(股)製「Cyclomer」(註冊商標)P(ACA)Z250(二丙二醇單甲基醚45質量%溶液、酸價110mgKOH/g、重量平均分子量20,000)；ADEKA(股)製「ADEKA ARKLS」WR301(二丙二醇單甲基醚45質量%溶液、酸價100mgKOH/g、重量平均分子量5,900)、KRX-3802(二丙二醇單甲基醚45質量%溶液、酸價80mgKOH/g、重量平均分子量5,500)鹼可溶性卡多樹脂(Cardo resin)等。 Examples of alkali-soluble resins having an ethylenically unsaturated group in the side chain include: Daicel-Allnex Co., Ltd. "Cyclomer" (registered trademark) P(ACA) Z250 (dipropylene glycol monomethyl ether 45 mass % solution, acid value 110 mgKOH/g, weight average molecular weight 20,000); ADEKA Co., Ltd. product "ADEKA ARKLS" WR301 (dipropylene glycol monomethyl ether 45 mass % solution, acid value 100mgKOH/g, weight average molecular weight 5,900), KRX-3802 (dipropylene glycol monomethyl ether 45% by mass solution, acid value 80mgKOH/g, weight average molecular weight 5,500) alkali-soluble Cardo resin, etc.

作為具有胺基甲酸酯鍵結之鹼可溶性樹脂，例如可列舉：Taisei Fine Chemical(股)製「Acrit(註冊商標)」8UA-017(乙酸乙酯50質量%溶液、11mgKOH/g、重量平均分子量40000)。 As an alkali-soluble resin which has a urethane bond, Taisei Fine Chemical Co., Ltd. product "Acrit (registered trademark)" 8UA-017 (50 mass % solution of ethyl acetate, 11 mgKOH/g, weight average molecular weight 40000) is mentioned, for example.

在本發明中，鹼可溶性樹脂係以具有A)下述通式(5)所示之結構單元、B)下述通式(6)所示之結構單元、與C)下述通式(7)所示之結構單元為較佳。藉由具有通式(5)所示之結構單元，可提升樹脂對於鹼顯影液之溶 解性，又，可抑制在曝光步驟中的不均。又，藉由具有通式(6)所示之結構單元，可因導入側鏈之乙烯性不飽和基而提升曝光及顯影之感度與光間隔物之彈性恢復率。又，藉由具有通式(7)所示之結構單元，可抑制透鏡掃描曝光所致之光間隔物之高度的偏差。 In the present invention, the alkali-soluble resin has A) a structural unit represented by the following general formula (5), B) a structural unit represented by the following general formula (6), and C) a structural unit represented by the following general formula (7). By having the structural unit represented by the general formula (5), the solubility of the resin in an alkaline developing solution can be improved, and unevenness in the exposure step can be suppressed. Moreover, by having the structural unit represented by the general formula (6), the sensitivity to exposure and development and the elastic recovery rate of the photo-spacer can be improved due to the introduction of ethylenically unsaturated groups in side chains. Moreover, by having the structural unit represented by General formula (7), the variation in the height of the photo-spacer by lens scanning exposure can be suppressed.

在此，R¹⁵表示氫原子或甲基。 Here, R ¹⁵ represents a hydrogen atom or a methyl group.

在此，R¹⁶及R¹⁷分別獨立表示氫原子或甲基。X表示-CH₂CH(OH)CH₂O(C=O)-、-CH₂CH₂NH(C=O)O(CH₂)_mO(C=O)-或-(CH₂)_nO(C=O)NHCH₂CH₂O(C=O)-。此外，m及n分別獨立表示1~4之整數。其中，X係以-CH₂CH(OH)CH₂O(C=O)-為較佳。 Here, R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group. X represents -CH ₂ CH(OH)CH ₂ O(C=O)-, -CH ₂ CH ₂ NH(C=O)O(CH ₂ ) _m O(C=O)-, or -(CH ₂ ) _n O(C=O)NHCH ₂ CH ₂ O(C=O)-. In addition, m and n each independently represent the integer of 1-4. Among them, X is preferably -CH ₂ CH(OH)CH ₂ O(C=O)-.

在此，Y表示可具有取代基的骨架碳數6~11之芳基、可具有取代基的骨架碳數7~10之芳烷基或可具有取代基的骨架碳數3~10之環烷基。在此，可使用的取代基係與在通式(1)及通式(2)之R¹~R³、R⁷~R⁸中說明之取代基相同。又，鹼可溶性樹脂之全結構單元中，作為重複單元之通式(5)、通式(6)及通式(7)係以佔有70莫耳%以上100莫耳%以下為較佳。 Here, Y represents an optionally substituted aryl group having 6 to 11 carbon atoms in the skeleton, an optionally substituted aralkyl group having 7 to 10 carbon atoms in the skeleton, or an optionally substituted cycloalkyl group having 3 to 10 carbon atoms in the skeleton. Here, usable substituents are the same as those described for R ¹ to R ³ , R ⁷ to R ⁸ in general formula (1) and general formula (2). In addition, among the total structural units of the alkali-soluble resin, the repeating units of the general formula (5), general formula (6) and general formula (7) are preferably more than 70 mol% and less than 100 mol%.

具有該通式(5)、通式(6)及通式(7)所示之結構單元的鹼可溶性樹脂，可藉由使用包含具有對應的側鏈結構之不飽和雙鍵單元的化合物並使其聚合而得。可進一步共聚合其他成分。 The alkali-soluble resin having the structural units represented by the general formula (5), general formula (6) and general formula (7) can be obtained by polymerizing a compound containing an unsaturated double bond unit having a corresponding side chain structure. Other components may be further copolymerized.

作為賦予前述通式(6)所示之結構單元的共聚成分，例如可列舉：(甲基)丙烯酸；(甲基)丙烯酸環氧丙酯、甲基丙烯酸2-異氰酸基乙酯、(甲基)丙烯酸2-羥基乙酯等。此等可使用2種以上。此等之中，又以在(甲基)丙烯酸加成(甲基)丙烯酸環氧丙酯為較佳。 Examples of the copolymerization component imparting the structural unit represented by the general formula (6) include (meth)acrylic acid; glycidyl (meth)acrylate, 2-isocyanatoethyl methacrylate, and 2-hydroxyethyl (meth)acrylate. These can use 2 or more types. Among them, adding glycidyl (meth)acrylate to (meth)acrylic acid is preferable.

作為賦予前述通式(7)所示之結構單元的共聚成分，例如可列舉：N-苄基馬來醯亞胺、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺等。此等可使用2種以上。此等之中，又以N-環己基馬來醯亞胺為較佳。 As a copolymerization component which imparts the structural unit represented by the said general formula (7), N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide etc. are mentioned, for example. These can use 2 or more types. Among them, N-cyclohexylmaleimide is more preferable.

作為其他共聚成分，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸2-羥基乙酯、(甲 基)丙烯酸苄酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸異莰酯等不飽和羧酸烷基酯；丙烯酸胺基乙酯等不飽和羧酸胺基烷基酯、鄰苯二甲酸單(2-(甲基)丙烯醯氧乙基)酯等多價羧酸單酯；苯乙烯、對甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、α-甲基苯乙烯等芳香族乙烯基化合物；乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯；(甲基)丙烯腈、α-氯(甲基)丙烯腈等氰化乙烯基化合物；1,3-丁二烯、異戊二烯等脂肪族共軛二烯；(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基)丙烯酸三環癸酯、三環癸烷二甲醇二(甲基)丙烯酸酯等具有三環癸烷骨架或二環戊二烯骨架之乙烯性不飽和化合物；巴豆酸、乙烯基乙酸等單羧酸或其酸酐；伊康酸、馬來酸、富馬酸等二羧酸或其酸酐等。 Examples of other copolymerization components include unsaturated carboxylic acid alkyl groups such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, secondary butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, n-pentyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, benzyl (meth)acrylate, and isobornyl (meth)acrylate. esters; unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, polyvalent carboxylic acid monoesters such as mono(2-(meth)acryloxyethyl) phthalate; aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene; vinyl carboxylates such as vinyl acetate and vinyl propionate; vinyl cyanide compounds such as (meth)acrylonitrile and α-chloro(meth)acrylonitrile; Dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate and other ethylenically unsaturated compounds with a tricyclodecane skeleton or a dicyclopentadiene skeleton; monocarboxylic acids such as crotonic acid and vinyl acetic acid or their anhydrides; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid or their anhydrides.

在本發明所使用之鹼可溶性樹脂中，其乙烯性不飽和基當量為400g/mol以下係因易於提升彈性恢復率而較佳。鹼可溶性樹脂之乙烯性不飽和基當量係以360g/mol以下為進一步較佳。例如：具有乙烯性不飽和基之B)前述通式(6)所示之結構單元的含有比率愈高，可愈縮小乙烯性不飽和基當量。鹼可溶性樹脂之乙烯性不飽和基當量可藉由具有乙烯性不飽和基之化合物的共聚合比而調整為所欲的範圍。此外，乙烯性不飽和基當量可藉由JIS K 0070：1992之試驗方法第6.0項所記載之方法，利用測定碘價而算出。 Among the alkali-soluble resins used in the present invention, the ethylenically unsaturated group equivalent is preferably not more than 400 g/mol because it is easy to increase the elastic recovery rate. The ethylenically unsaturated group equivalent of the alkali-soluble resin is more preferably 360 g/mol or less. For example: B) having an ethylenically unsaturated group The higher the content ratio of the structural unit represented by the aforementioned general formula (6), the smaller the ethylenically unsaturated group equivalent can be reduced. The ethylenically unsaturated group equivalent of alkali-soluble resin can be adjusted to a desired range by the copolymerization ratio of the compound which has an ethylenically unsaturated group. In addition, the ethylenically unsaturated group equivalent can be calculated by measuring the iodine value according to the method described in JIS K 0070: 1992 test method item 6.0.

在本發明所使用之鹼可溶性樹脂中，其重量平均分子量(「Mw」)係以3,000~100,000為較佳。藉由 將Mw設為3,000以上，可提高預焙膜之黏度，即使是利用透鏡掃描方式進行曝光之情形，亦可更抑制高度之偏差。Mw係以20,000以上為更佳。另一方面，藉由將Mw設為100,000以下，可抑制圖案表面之凹凸，提升圖案之表面形狀。Mw係以80,000以下為更佳。在此，本發明中的鹼可溶性樹脂之Mw係藉由標準聚苯乙烯的換算值，可使用凝膠滲透層析而測定。 In the alkali-soluble resin used in the present invention, the weight average molecular weight ("Mw") is preferably 3,000~100,000. By setting Mw to 3,000 or more, the viscosity of the prebaked film can be increased, and even in the case of exposure by lens scanning method, the variation in height can be further suppressed. More than 20,000 is better for Mw. On the other hand, by setting Mw to be 100,000 or less, unevenness on the surface of the pattern can be suppressed, and the surface shape of the pattern can be improved. Mw is better below 80,000. Here, the Mw of the alkali-soluble resin in this invention is a value converted from standard polystyrene, and can be measured using gel permeation chromatography.

在本發明所使用之鹼可溶性樹脂中，其酸價係以60~100mgKOH/g為較佳。藉由將酸價設為60mgKOH/g以上，可更降低高度偏差。酸價係以65mgKOH/g以上為更佳。另一方面，藉由將酸價設為100mgKOH/g以下，可抑制圖案表面之凹凸，提升圖案之表面形狀。酸價係以95mgKOH/g以下為更佳。鹼可溶性樹脂之酸價可藉由具有羧基之化合物的共聚合比而調整為所欲的範圍。在此，本發明中的鹼可溶性樹脂之酸價可藉由JIS K 0070：1992之試驗方法第3.1項的中和滴定法而求出。此外，當使用固體成分濃度30質量%左右的鹼可溶性樹脂溶液而測定時，可藉由將5g的鹼可溶性樹脂溶液放入鋁製杯子(

45mm)，在130℃下加熱1小時以去除溶劑，而得到測定所需要的量之鹼可溶性樹脂。 In the alkali-soluble resin used in the present invention, the acid value is preferably 60-100 mgKOH/g. By setting the acid value to 60 mgKOH/g or more, height variations can be further reduced. The acid value is more than 65mgKOH/g. On the other hand, by setting the acid value to 100 mgKOH/g or less, it is possible to suppress unevenness on the surface of the pattern and improve the surface shape of the pattern. The acid value is better below 95mgKOH/g. The acid value of the alkali-soluble resin can be adjusted to a desired range by the copolymerization ratio of the compound having a carboxyl group. Here, the acid value of the alkali-soluble resin in this invention can be calculated|required by the neutralization titration method of the test method item 3.1 of JISK0070:1992. In addition, when measuring using an alkali-soluble resin solution with a solid content concentration of about 30% by mass, it can be measured by putting 5 g of the alkali-soluble resin solution in an aluminum cup (

45 mm), heated at 130° C. for 1 hour to remove the solvent, and obtain the amount of alkali-soluble resin required for the measurement.

本發明之感光性樹脂組成物所包含之鹼可溶性樹脂的含量，係以設為固體成分中10~45質量%為較佳。藉由將鹼可溶性樹脂之該含量設為10質量%以上，可更抑制間隔物之高度的偏差。另一方面，藉由將鹼可 溶性樹脂之該含量設為45質量%以下，可更提升彈性恢復率。 The content of the alkali-soluble resin contained in the photosensitive resin composition of the present invention is preferably 10 to 45% by mass in the solid content. By making this content of alkali-soluble resin 10 mass % or more, the variation of the height of a spacer can be suppressed more. On the other hand, by setting the content of the alkali-soluble resin to 45% by mass or less, the elastic recovery rate can be further improved.

本發明所使用之光聚合起始劑，係指藉由放射線(包含可見光、紫外線及電子束)而分解及/或反應，產生自由基之化合物。作為光聚合起始劑，例如可列舉：肟酯系化合物、烷基苯酮系化合物、二苯基酮系化合物、噻噸酮系化合物、咪唑系化合物、苯并噻唑系化合物、苯并

唑系化合物、醯基膦氧化物系化合物、二茂鈦系化合物等。可含有此等2種以上。 The photopolymerization initiator used in the present invention refers to a compound that generates free radicals by decomposing and/or reacting with radiation (including visible light, ultraviolet rays, and electron beams). Examples of photopolymerization initiators include oxime ester compounds, alkylphenone compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, benzothiazole compounds, benzothiazole compounds, and

Azole-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, and the like. These 2 or more types may be contained.

作為肟酯系化合物，例如可列舉：1,2-辛二酮，1-[4-(苯硫基)-,2-(O-苯甲醯基肟)]、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、乙酮，1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、乙酮，1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧戊環基)甲氧基苯甲醯基}-9H-咔唑-3-基]-,1-(O-乙醯基肟)、「ADEKA ARKLS」(註冊商標)N-1919、NCI-831、NCI-930(以上皆為ADEKA(股)製)、「Irgacure」(註冊商標)OXE01、OXE02、OXE03、OXE04(以上皆為BASF Japan(股)製)等。作為烷基苯酮系化合物，例如可列舉：2,2-二乙氧基苯乙酮、2-苄基-2-二甲基胺基-1-(4-N-

啉基苯基)-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮、α-羥基異丁基苯酮、1-羥基-環己基-苯基-酮、2-羥基-2-甲基-1-苯基-丙-1-酮、「Irgacure」(註冊商標)907(BASF Japan(股)製)等。作為二苯基酮系化合 物，例如可列舉：二苯基酮、N,N’-四乙基-4,4’-二胺基二苯基酮、4-甲氧基-4’-二甲基胺基二苯基酮等。作為噻噸酮系化合物，例如可列舉：噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮、1-氯-4-丙基噻噸酮、1-羥基環己基苯基酮等。作為咪唑系化合物，例如可列舉：2-(鄰氯苯基)-4,5-二苯基咪唑二聚物等。作為苯并噻唑系化合物，例如可列舉：2-巰基苯并噻唑等。作為苯并

唑系化合物，例如可列舉：2-巰基苯并

唑等。作為醯基膦氧化物系化合物，例如可列舉：2,4,6-三甲基苯甲醯基-二苯基-膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物等。作為二茂鈦系化合物，例如可列舉：雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等。從更提升感度的觀點來看，此等之中又以肟酯系化合物、烷基苯酮系化合物為較佳。肟酯系化合物之中又以「ADEKA ARKLS」(註冊商標)N-1919為更佳，烷基苯酮系化合物之中又以「Irgacure」(註冊商標)907為更佳。 Examples of oxime ester compounds include: 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxy) Benzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-,1-(O-acetyl oxime), "ADEKA ARKLS" (registered trademark) N-1 919, NCI-831, NCI-930 (the above are all made by ADEKA Co., Ltd.), "Irgacure" (registered trademark) OXE01, OXE02, OXE03, OXE04 (the above are all made by BASF Japan Co., Ltd.), etc. Examples of alkylphenone compounds include 2,2-diethoxyacetophenone, 2-benzyl-2-dimethylamino-1-(4-N-

Linylphenyl)-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Linyl)phenyl]-1-butanone, α-hydroxyisobutylbenzophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, "Irgacure" (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.), etc. Examples of the diphenyl ketone compound include diphenyl ketone, N,N'-tetraethyl-4,4'-diaminodiphenyl ketone, 4-methoxy-4'-dimethylamino diphenyl ketone, and the like. Examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 1-chloro-4-propylthioxanthone, and 1-hydroxycyclohexyl phenyl ketone. As an imidazole compound, a 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer etc. are mentioned, for example. As a benzothiazole compound, 2-mercaptobenzothiazole etc. are mentioned, for example. as benzo

Azole compounds, for example, 2-mercaptobenzo

azole etc. Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like. Examples of the titanocene compound include bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium and the like. Among these, oxime ester-based compounds and alkylphenone-based compounds are more preferable from the viewpoint of improving sensitivity. Among oxime ester compounds, "ADEKA ARKLS" (registered trademark) N-1919 is more preferable, and among alkylphenone-based compounds, "Irgacure" (registered trademark) 907 is more preferable.

在本發明中，感光性樹脂組成物所包含之光聚合起始劑的含量，係以設為固體成分中1~30質量%為較佳，2~25質量%為進一步較佳。若為30質量%以下，則易於提高乙烯性不飽和基當量與胺基甲酸酯當量。若為1質量%以上，則易於提高感度。 In the present invention, the content of the photopolymerization initiator included in the photosensitive resin composition is preferably 1 to 30% by mass in the solid content, and more preferably 2 to 25% by mass. If it is 30 mass % or less, it will become easy to increase ethylenic unsaturated group equivalent and urethane equivalent. When it is 1 mass % or more, it will become easy to raise a sensitivity.

本發明之感光性樹脂組成物可含有：填料、增感助劑、紫外線吸收劑、密合改良劑、界面活性劑、 聚合抑制劑、前述鹼可溶性樹脂以外之高分子化合物、有機酸、有機胺基化合物、硬化劑等添加劑、溶劑。 The photosensitive resin composition of the present invention may contain fillers, sensitizers, ultraviolet absorbers, adhesion improvers, surfactants, polymerization inhibitors, polymer compounds other than the aforementioned alkali-soluble resins, organic acids, organic amino compounds, additives such as hardeners, and solvents.

本發明之感光性樹脂組成物藉由含有填料，可更提高預焙膜之乾燥後的黏度，更抑制高度偏差。作為填料，例如可列舉：二氧化矽、氧化鋁、二氧化鈦、硫酸鋇等無機氧化物粒子；金屬粒子；丙烯酸、苯乙烯、聚矽氧、含有氟的聚合物等樹脂粒子等。可含有此等2種以上。從粒徑與分散性的觀點來看，此等之中又以使用二氧化矽粒子為較佳。利用填料之比表面積換算的平均粒徑係以4~120nm為較佳。若填料之平均粒徑為4nm以上，則可更抑制作成間隔物時之高度的偏差。另一方面，若粒徑為120nm以下，則可抑制經過光蝕刻步驟所得之間隔物圖案的表面之凹凸，提升圖案之表面形狀。 The photosensitive resin composition of the present invention can further increase the viscosity of the prebaked film after drying and further suppress height deviation by containing fillers. Examples of the filler include inorganic oxide particles such as silica, alumina, titanium dioxide, and barium sulfate; metal particles; and resin particles such as acrylic, styrene, silicone, and fluorine-containing polymers. These 2 or more types may be contained. From the viewpoint of particle size and dispersibility, among these, it is more preferable to use silica particles. The average particle size converted from the specific surface area of the filler is preferably 4-120 nm. When the average particle diameter of the filler is 4 nm or more, it is possible to further suppress variation in height when forming a spacer. On the other hand, if the particle size is 120 nm or less, the unevenness of the surface of the spacer pattern obtained through the photoetching step can be suppressed, and the surface shape of the pattern can be improved.

當不含有填料時，易於提高樹脂中的乙烯性不飽和基當量及胺基甲酸酯當量而較佳。 When the filler is not contained, the ethylenically unsaturated group equivalent and the urethane equivalent in the resin are easy to increase, which is preferable.

本發明之感光性樹脂組成物藉由含有增感助劑，可提升感度。作為增感助劑，例如可列舉：芳香族或脂肪族之三級胺等。 The photosensitive resin composition of the present invention can enhance sensitivity by containing a sensitizer. As a sensitizer, an aromatic or aliphatic tertiary amine etc. are mentioned, for example.

本發明之感光性樹脂組成物藉由含有紫外線吸收劑，可輕易形成透明性高、細微且錐度短的光間隔物。作為紫外線吸收劑，從透明性及非著色性的觀點來看，係以苯并***系化合物、二苯基酮系化合物、三

系化合物等有機化合物系紫外線吸收劑為較佳。可含有此等2種以上。此等之中，又以苯并***系化合物為較佳。 The photosensitive resin composition of the present invention can easily form a highly transparent, fine and short-tapered photo-spacer by containing an ultraviolet absorber. As ultraviolet absorbers, from the viewpoint of transparency and non-coloring properties, benzotriazole-based compounds, benzophenone-based compounds, three

Organic compound-based ultraviolet absorbers such as organic compounds are preferred. These 2 or more types may be contained. Among these, benzotriazole-based compounds are preferred.

作為苯并***系化合物，例如可列舉：2-(2H-苯并***-2-基)-對甲酚、2-(2H-苯并***-2-基)-4-6-雙(1-甲基-1-苯基乙基)苯酚、2-[5-氯(2H)-苯并***-2-基]-4-甲基-6-(三級丁基苯酚)、2,4-二-三級丁基-6-(5-氯苯并***-2-基)苯酚、2-(2H-苯并***-2-基)苯酚、2-(2H-苯并***-2-基)-4,6-三級戊基苯酚、2-(2H-苯并***-2-基-4-(1,1,3,3-四甲基丁基)苯酚、2(2H-苯并***-2-基)-6-十二基-4-甲基苯酚、2[2-羥基-3-(3,4,5,6-四氫鄰苯二甲醯亞胺-甲基)-5-甲基苯基]苯并***等。 Examples of benzotriazole-based compounds include: 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol, 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tertiary butylphenol), 2,4-di-tertiary butyl-6-(5-chlorobenzo Triazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-tertiary pentylphenol, 2-(2H-benzotriazol-2-yl-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2[2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl)-5-methylphenyl]benzotriazole, etc.

作為二苯基酮系化合物，例如可列舉：辛基苯(Octabenzone)、2-羥基-4-正辛氧基二苯基酮等。 Examples of the diphenyl ketone compound include octylbenzene (octabenzone), 2-hydroxy-4-n-octyloxydiphenyl ketone, and the like.

作為三

系化合物，例如可列舉：2-(4,6-二苯基-1,3,5-三

-2-基)-5-[(己基)氧基]-苯酚。 as three

series compounds, such as: 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-[(hexyl)oxy]-phenol.

本發明之感光性樹脂組成物可包含之紫外線吸收劑的含量，係以固體成分中0.3~10質量%為較佳。藉由將紫外線吸收劑之含量設為0.3質量%以上，可更縮短錐部。紫外線吸收劑之含量係以2質量%以上為更佳。另一方面，藉由將紫外線吸收劑之含量設為10質量%以下，可高度維持感度。紫外線吸收劑之含量係以8質量%以下為更佳。此外，固體成分係指除了感光性樹脂組成物所包含之溶劑以外的成分。 The content of the ultraviolet absorber that the photosensitive resin composition of the present invention may contain is preferably 0.3-10% by mass in the solid content. By making content of an ultraviolet absorber 0.3 mass % or more, a taper part can be shortened further. The content of the ultraviolet absorber is more preferably 2% by mass or more. On the other hand, high sensitivity can be maintained by making content of an ultraviolet absorber into 10 mass % or less. The content of the ultraviolet absorber is more preferably 8% by mass or less. In addition, solid content means the component other than the solvent contained in the photosensitive resin composition.

作為前述密合改良劑，例如可列舉：乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3- 胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-脲基丙基三烷氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷等矽烷偶合劑等。此等可含有2種以上。又，係以使用具有胺基甲酸酯鍵結、或具有胺基甲酸酯鍵結形成能之化合物為較佳，作為這樣的化合物，可列舉：3-脲基丙基三烷氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷之季戊四醇四丙烯酸酯加成物。 Examples of the adhesion improving agent include: vinyltrimethoxysilane, vinyltriethoxysilane, vinylginseng(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-iso Silane coupling agents such as cyanate propyltriethoxysilane, etc. These may contain 2 or more types. Also, it is preferable to use a compound having a urethane bond or a urethane bond-forming ability, and examples of such compounds include pentaerythritol tetraacrylate adducts of 3-ureidopropyltrialkoxysilane and 3-isocyanatepropyltriethoxysilane.

本發明之感光性樹脂組成物可包含之密合改良劑的含量，係以固體成分中0.1~20質量%為較佳。藉由將密合改良劑之含量設為0.1質量%以上，可提升顯影密合性。密合改良劑之含量係以0.5質量%以上為更佳。另一方面，藉由將密合改良劑之含量設為20質量%以下，可抑制鹼可溶性樹脂、聚合性化合物之凝集。密合改良劑之含量係以10質量%以下為更佳。 The content of the adhesion improving agent that can be included in the photosensitive resin composition of the present invention is preferably 0.1-20% by mass in the solid content. Image development adhesiveness can be improved by making content of an adhesion improving agent 0.1 mass % or more. The content of the adhesion improving agent is more preferably 0.5% by mass or more. On the other hand, aggregation of an alkali-soluble resin and a polymeric compound can be suppressed by making content of an adhesion improving agent 20 mass % or less. The content of the adhesion improver is more preferably 10% by mass or less.

作為前述界面活性劑，例如可列舉：月桂硫酸銨、聚氧乙烯烷基醚硫酸三乙醇胺等陰離子界面活性劑；硬脂胺乙酸酯、月桂基三甲基銨氯化物等陽離子界面活性劑；月桂基二甲基胺氧化物、月桂基羧基甲基羥基乙基咪唑鎓甜菜鹼等兩性界面活性劑；聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、山梨醇酐單硬脂酸酯等非離 子界面活性劑；全氟丁基磺酸鹽、含有全氟烷基的羧酸鹽、含有全氟烷基的三甲基銨鹽、含有全氟烷基的磷酸酯、或全氟烷基環氧乙烷加成物等氟系界面活性劑；聚醚變性聚甲基烷基矽氧烷、聚醚變性聚二甲基矽氧烷、聚酯變性聚二甲基矽氧烷、聚酯變性甲基烷基聚矽氧烷、芳烷基變性聚甲基烷基矽氧烷、含有聚醚變性羥基的聚二甲基矽氧烷、含有聚酯變性羥基的聚二甲基矽氧烷等聚矽氧系界面活性劑等。可含有此等2種以上。此等之中，又以聚醚變性聚二甲基矽氧烷「BYK」(註冊商標)333(BYK-Chemie公司製)為較佳。 Examples of the aforementioned surfactant include: anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; amphoteric surfactants such as lauryldimethylamine oxide and lauryl carboxymethylhydroxyethylimidazolium betaine; Fluorine-based surfactants such as carboxylates containing perfluoroalkyl groups, trimethylammonium salts containing perfluoroalkyl groups, phosphate esters containing perfluoroalkyl groups, or perfluoroalkyl ethylene oxide adducts; polyether-modified polymethylalkylsiloxanes, polyether-modified polydimethylsiloxanes, polyester-modified polydimethylsiloxanes, polyester-modified methylalkylpolysiloxanes, aralkyl-modified polymethylalkylsiloxanes, polyether-modified hydroxyl-containing polydimethylsiloxanes, polyester-modified hydroxyl-containing polydimethylsiloxanes, etc. Polysiloxane-based surfactants, etc. These 2 or more types may be contained. Among them, polyether-modified polydimethylsiloxane "BYK" (registered trademark) 333 (manufactured by BYK-Chemie) is preferable.

本發明之感光性樹脂組成物可包含之界面活性劑的含量，係以固體成分中0.001~10質量%為較佳。藉由將界面活性劑之含量設為0.001質量%以上，可提升感光性樹脂組成物之塗布性。界面活性劑之含量係以0.01質量%以上為更佳。另一方面，藉由將界面活性材之含量設為10質量%以下，可抑制圖案表面之凹凸，提升圖案之表面形狀。界面活性劑之含量係以1質量%以下為更佳。 The content of the surfactant that may be included in the photosensitive resin composition of the present invention is preferably 0.001-10% by mass in the solid content. Coatability of the photosensitive resin composition can be improved by making content of surfactant into 0.001 mass % or more. The content of the surfactant is more preferably 0.01% by mass or more. On the other hand, by setting the content of the interface active material to 10% by mass or less, it is possible to suppress unevenness on the surface of the pattern and improve the surface shape of the pattern. The content of the surfactant is more preferably 1% by mass or less.

作為前述聚合抑制劑，例如可列舉：氫醌、三級丁基氫醌、2,5-雙(1,1,3,3-四甲基丁基)氫醌、2,5-雙(1,1-二甲基丁基)等氫醌系聚合抑制劑；兒茶酚、三級丁基兒茶酚等兒茶酚系聚合抑制劑等。聚合抑制劑可含有2種以上。 Examples of the polymerization inhibitor include: hydroquinone-based polymerization inhibitors such as hydroquinone, tertiary butylhydroquinone, 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone, and 2,5-bis(1,1-dimethylbutyl); catechol-based polymerization inhibitors such as catechol and tertiary butylcatechol; and the like. A polymerization inhibitor may contain 2 or more types.

本發明之感光性樹脂組成物可包含之聚合抑制劑的含量，係以固體成分中0.01~0.5質量%為較佳。 藉由將聚合抑制劑之含量設為0.01質量%以上，可提升感光性樹脂組成物之經時保存安定性。另一方面，藉由將聚合抑制劑之含量設為0.5質量%以下，可抑制浸漬於極性溶劑時的感度降低所致之膜表面的侵蝕、斑點的發生。 The content of the polymerization inhibitor that can be included in the photosensitive resin composition of the present invention is preferably 0.01-0.5% by mass in the solid content. By making content of a polymerization inhibitor 0.01 mass % or more, the temporal storage stability of a photosensitive resin composition can be improved. On the other hand, by making content of a polymerization inhibitor into 0.5 mass % or less, the erosion of the film surface by the sensitivity reduction at the time of immersion in a polar solvent, and generation|occurrence|production of a spot can be suppressed.

作為前述鹼可溶性樹脂以外之高分子化合物，例如可列舉：其單獨幾乎不溶解於鹼顯影液的丙烯酸樹脂、醇酸樹脂、三聚氰胺樹脂、聚乙烯醇、聚酯、聚醚、聚醯胺、聚醯胺醯亞胺、聚醯亞胺、聚醯亞胺前驅物等。該高分子化合物可使用2種以上。 Examples of polymer compounds other than the aforementioned alkali-soluble resins include acrylic resins, alkyd resins, melamine resins, polyvinyl alcohols, polyesters, polyethers, polyamides, polyamideimides, polyimides, and polyimide precursors that are hardly soluble in alkaline developing solutions alone. Two or more types of such polymer compounds can be used.

作為前述溶劑，可列舉：醚系溶劑、酯系溶劑、醇系溶劑、酮系溶劑、二甲苯、乙苯、溶劑油等。溶劑可使用2種以上。 Examples of the solvent include ether solvents, ester solvents, alcohol solvents, ketone solvents, xylene, ethylbenzene, mineral spirits, and the like. Two or more kinds of solvents can be used.

作為醚系溶劑，例如可列舉：丙二醇單甲基醚、丙二醇單乙基醚、丙二醇三級丁基醚、二乙二醇甲基乙基醚、二丙二醇單甲基醚等。此等之中又以丙二醇單甲基醚、丙二醇單乙基醚、二乙二醇甲基乙基醚為較佳。 Examples of ether solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, and the like. Among these, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and diethylene glycol methyl ethyl ether are more preferable.

作為酯系溶劑，例如可列舉：乙酸苄酯、苯甲酸乙酯、γ-丁內酯、苯甲酸甲酯、丙二酸二乙酯、乙酸2-乙基己酯、乙酸2-丁氧基乙酯、乙酸3-甲氧基-丁酯、乙酸3-甲氧基-3-甲基-丁酯、乙二酸二乙酯、乙醯乙酸乙酯、乙酸3-甲氧基-丁酯、乙醯乙酸甲酯、丙酸乙基-3-乙氧酯、乙酸2-乙基丁酯、丙酸異戊酯、丙二醇單甲基醚丙酸酯、丙二醇單乙基醚乙酸酯、乙酸戊酯、丙 二醇單甲基醚乙酸酯、丙二醇單乙基醚、丙二醇三級丁基醚、二丙二醇單甲基醚乙酸酯、乙酸乙酯、乙酸丁酯、乙酸異戊酯等。此等之中又以乙酸3-甲氧基-丁酯、丙二醇單乙基醚乙酸酯、丙二醇單甲基醚丙酸酯等為較佳。 Examples of ester-based solvents include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-butyl acetate, 3-methoxy-3-methyl-butyl acetate, diethyl oxalate, ethyl acetoacetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3 propionate - Ethoxylate, 2-ethylbutyl acetate, isoamyl propionate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether acetate, amyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isoamyl acetate, etc. Among them, 3-methoxy-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, etc. are more preferable.

作為醇系溶劑，例如可列舉：丁醇、3-甲基-2-丁醇、3-甲基-3-甲氧基丁醇。 Examples of the alcohol-based solvent include butanol, 3-methyl-2-butanol, and 3-methyl-3-methoxybutanol.

作為酮系溶劑，例如可列舉：環戊酮、環己酮。 As a ketone solvent, cyclopentanone and cyclohexanone are mentioned, for example.

本發明之感光性樹脂組成物係以成形為上底面之直徑為6μm、下底面之直徑為9μm、高度為3μm的圓錐台狀，施加50mN的負重時之彈性恢復率為60%以上為較佳。此外，詳細的成形條件係如實施例之項目所記載。若該彈性恢復率為60%以上，則可更抑制晶胞壓接時之間隔物的高度之偏差，更降低光間隔物的塑性變形所致之顯示不均。該彈性恢復率係以70%以上為更佳。彈性恢復率愈接近100%，愈可更抑制光間隔物的變形所致之對於液晶間隙的影響、與其所致之顯示不均。上述形狀係光間隔物之代表性的形狀，上述負重係光間隔物在製造或使用時所受的負重之一例。藉由該方法，可相對地評價為了形成光間隔物所使用之感光性樹脂組成物的難以塑性變形之程度。 The photosensitive resin composition of the present invention is formed into a truncated conical shape with a diameter of 6 μm on the top surface, a diameter of 9 μm on the bottom surface, and a height of 3 μm. The elastic recovery rate is preferably 60% or more when a load of 50 mN is applied. In addition, the detailed molding conditions are as described in the item of an Example. If the elastic recovery rate is more than 60%, the variation in the height of the spacers during the unit cell crimping can be further suppressed, and the display unevenness caused by the plastic deformation of the photo-spacers can be further reduced. The elastic recovery rate is more than 70%. The closer the elastic recovery rate is to 100%, the more it can suppress the influence of the deformation of the photo-spacer on the liquid crystal gap and the display unevenness caused by it. The said shape is a typical shape of a photo-spacer, and the said load is an example of the load which a photo-spacer receives at the time of manufacture or use. By this method, the degree of plastic deformation resistance of the photosensitive resin composition used for forming a photo-spacer can be relatively evaluated.

在圖1顯示表示光間隔物之彈性特性的遲滯曲線之一例的示意圖。若在光間隔物施加負重、又去除負重，則可得到如圖1所示，施加在光間隔物之負重、與光間隔物之變形量的遲滯曲線。藉由從遲滯曲線求出 光間隔物之總變形量Ha[μm]、塑性變形量Hb[μm]及彈性變形量，可算出光間隔物之彈性恢復率(((Ha-Hb)/Ha)×100)(%)。在此，遲滯曲線可藉由使用硬度計Fischer(Fischerscope H100；Helmut Fischer GmbH & Co公司製)與

50μm的平面型壓頭，以速度2.5mN/秒施加壓力直到到達負重50mN後，以速度2.5mN/秒釋放而得。 FIG. 1 shows a schematic diagram showing an example of a hysteresis curve of the elastic properties of a photo-spacer. If a load is applied to the photo-spacer and then removed, the hysteresis curve of the load applied to the photo-spacer and the deformation of the photo-spacer can be obtained as shown in Figure 1. By calculating the total deformation Ha[μm], plastic deformation Hb[μm] and elastic deformation of the photo-spacer from the hysteresis curve, the elastic recovery rate (((Ha-Hb)/Ha)×100)(%) of the photo-spacer can be calculated. Here, the hysteresis curve can be obtained by using a hardness tester Fischer (Fischerscope H100; manufactured by Helmut Fischer GmbH & Co.) and

The 50μm flat indenter is obtained by applying pressure at a speed of 2.5mN/s until reaching a load of 50mN, and then releasing it at a speed of 2.5mN/s.

為了將形成光間隔物時之彈性恢復率設在上述範圍，係以使用乙烯性不飽和基當量在前述較佳範圍的感光性樹脂組成物為佳。 In order to set the elastic recovery rate when forming the photo-spacer within the above-mentioned range, it is preferable to use a photosensitive resin composition having an ethylenically unsaturated group equivalent within the above-mentioned preferred range.

本發明之感光性樹脂組成物可藉由以任意的比例混合鹼可溶性樹脂、光聚合起始劑及聚合性化合物、與因應需要的界面活性劑、聚合抑制劑、溶劑、紫外線吸收劑等其他添加劑而得。 The photosensitive resin composition of the present invention can be obtained by mixing an alkali-soluble resin, a photopolymerization initiator, a polymerizable compound, and other additives such as a surfactant, a polymerization inhibitor, a solvent, and an ultraviolet absorber as needed in any ratio.

本發明之感光性樹脂組成物可理想地使用於光間隔物之形成。 The photosensitive resin composition of the present invention can be ideally used in the formation of photo-spacers.

為了濾光片之高精細化，光間隔物之形狀係以圓錐台狀為較佳，上底之直徑係以15μm以下為較佳。又，相對於下底之直徑的上底之直徑的比(上底/下底)係以0.3~2.0為較佳。 For the high-definition of the optical filter, the shape of the optical spacer is preferably in the shape of a truncated cone, and the diameter of the upper base is preferably less than 15 μm. Also, the ratio of the diameter of the upper base to the diameter of the lower base (upper base/lower base) is preferably 0.3 to 2.0.

其次，針對本發明之光間隔物之製造方法，以形成在基板上之情形為例進行說明。係以將前述本發明之感光性樹脂組成物塗布於基板上，進行乾燥而得到預焙膜，對預焙膜進行透鏡掃描曝光及顯影，藉此形成光間隔物為較佳。再者，係以使顯影後的塗布膜圖案進行加熱處理而使其硬化為較佳。此外，本發明之光間隔 物並不只有直接接觸而設置於基板之情形，可設置在基板上所構成之各種元件(例如：黑矩陣、平坦化膜、電極、液晶配向膜)之上。 Next, with regard to the manufacturing method of the photo-spacer of the present invention, the case where it is formed on a substrate will be described as an example. It is better to apply the aforementioned photosensitive resin composition of the present invention on a substrate, dry it to obtain a prebaked film, and perform lens scanning exposure and development on the prebaked film to form photo-spacers. In addition, it is preferable to heat-process and harden the coating film pattern after image development. In addition, the photo-spacer of the present invention is not limited to direct contact with the substrate, but can be arranged on various components formed on the substrate (such as black matrix, planarization film, electrodes, liquid crystal alignment film).

作為基板，可列舉：玻璃、高分子薄膜等透明基板。 Examples of the substrate include transparent substrates such as glass and polymer films.

作為感光性樹脂組成物之塗布方法，例如可列舉：浸塗法、輥塗法、旋塗法、模具塗布法、線棒塗布法等。 As a coating method of the photosensitive resin composition, a dip coating method, a roll coating method, a spin coating method, a die coating method, a wire bar coating method, etc. are mentioned, for example.

作為乾燥方法，可列舉：減壓乾燥、使用烘箱、加熱板之加熱乾燥(預焙)等。減壓乾燥之情形，從抑制乾燥溶劑再凝縮至減壓腔內壁的觀點來看，加熱溫度係以100℃以下為較佳。減壓乾燥壓力係以感光性樹脂組成物所包含之溶劑的蒸氣壓以下為較佳，1~1000Pa為較佳。減壓乾燥時間係以10~600秒鐘為較佳。預焙之情形，通常加熱溫度為60~200℃，加熱時間為1~60分鐘。 As a drying method, drying under reduced pressure, heating drying (prebaking) using an oven or a hot plate, etc. are mentioned. In the case of drying under reduced pressure, the heating temperature is preferably 100° C. or lower from the viewpoint of preventing recondensation of the drying solvent to the inner wall of the reduced pressure chamber. The reduced-pressure drying pressure is preferably below the vapor pressure of the solvent contained in the photosensitive resin composition, preferably 1 to 1000 Pa. The drying time under reduced pressure is preferably 10 to 600 seconds. In the case of prebaking, the heating temperature is usually 60~200°C, and the heating time is 1~60 minutes.

在本發明中，利用下述製備方法所得之預焙膜在23℃下之黏度係以1×10³~1×10⁸Pa‧s為較佳。藉由對在23℃下之黏度為1×10³Pa‧s以上的預焙膜進行曝光，可適度地抑制預焙膜之流動性，更抑制在預焙膜之搬運步驟、曝光步驟、加熱乾燥(後焙)步驟中發生不均。在23℃下之黏度係以1×10⁵Pa‧s以上為更佳。另一方面，藉由對在23℃下之黏度為1×10⁸Pa‧s以下的預焙膜進行曝光，可提升顯影性。在此，預焙膜在23℃下之黏度係指：採取90mm³以上的預焙膜，使用流變計(MCR-302； Anton Paar(股)製)與

15mm的平板，在測定厚度：0.5mm、頻率：1Hz、歪斜：0.5%之條件下，一邊以0.083℃/秒之升溫速度從20℃升溫至110℃，一邊進行測定時之在23℃下之黏度。此外，在濾光片基板上製造光間隔物之步驟中，預焙膜之溫度係在乾燥步驟中加熱至100℃左右，而通常藉由曝光前的冷卻而成為室溫(約23℃)程度。因此，在本發明中，係作為通常的曝光時之預焙膜溫度，而著眼於在23℃下之黏度。 In the present invention, the viscosity of the prebaked film obtained by the following preparation method at 23°C is preferably 1×10 ³ ~1×10 ⁸ Pa‧s. By exposing a prebaked film with a viscosity of 1×10 ³ Pa‧s or higher at 23°C, the fluidity of the prebaked film can be moderately suppressed, and unevenness in the prebaked film’s handling step, exposure step, and heat-drying (post-baking) step can be suppressed. The viscosity at 23°C is more than 1×10 ⁵ Pa‧s. On the other hand, developability can be improved by exposing a prebaked film whose viscosity at 23°C is 1×10 ⁸ Pa‧s or less. Here, the viscosity of the prebaked film at 23°C refers to: take a prebaked film of 90mm3 ^or more, use a rheometer (MCR-302; manufactured by Anton Paar (Stock)) and

The viscosity of a 15mm flat plate at 23°C is measured under the conditions of thickness: 0.5mm, frequency: 1Hz, skew: 0.5%, while heating from 20°C to 110°C at a rate of 0.083°C/sec. In addition, in the step of manufacturing photo-spacers on the filter substrate, the temperature of the prebaked film is heated to about 100°C in the drying step, and is usually cooled to room temperature (about 23°C) by cooling before exposure. Therefore, in the present invention, attention is paid to the viscosity at 23° C. as the prebaked film temperature at the time of normal exposure.

係以對所得之預焙膜介隔光罩而進行曝光，藉此使曝光部分硬化，藉由鹼顯影液而進行顯影，藉此去除未曝光部分，形成圖案為較佳。 It is preferable to expose the obtained prebaked film through a mask to harden the exposed part, and develop it with an alkaline developer to remove the unexposed part and form a pattern.

作為曝光方式，例如可列舉：接近式曝光、透鏡掃描曝光、鏡面投影曝光、步進曝光等。在本發明中，可理想地使用針對大型基板之高精細圖案加工優異的透鏡掃描曝光。由於本發明之感光性樹脂組成物可抑制高度之偏差，因此即使是排列了1st透鏡與2nd透鏡之二列的透鏡，在該透鏡之接縫有曝光時間差，且因預焙膜會流動而易於發生高度之偏差的透鏡掃描曝光，亦可理想地使用作為裝置構成。作為透鏡掃描曝光裝置，例如可列舉：FX-65S(Nikon(股)製)。 As an exposure method, proximity exposure, lens scanning exposure, mirror projection exposure, step exposure etc. are mentioned, for example. In the present invention, lens scanning exposure excellent in high-definition pattern processing for large substrates can be ideally used. Since the photosensitive resin composition of the present invention can suppress height deviation, even if it is a lens arranged in two rows of 1st lens and 2nd lens, there is a difference in exposure time at the joint of the lens, and the lens scanning exposure that is prone to height deviation due to the flow of the prebaked film can also be ideally used as a device configuration. As a lens scanning exposure apparatus, FX-65S (made by Nikon Co., Ltd.) is mentioned, for example.

作為顯影步驟，係以藉由鹼顯影液的顯影為較佳。作為鹼顯影液，可列舉：有機鹼顯影液、無機鹼顯影液等。作為無機鹼顯影液，係以碳酸鈉、氫氧化鈉、氫氧化鉀之水溶液等為較佳。作為有機鹼顯影液，係以氫氧化四甲銨水溶液、甲醇胺等胺系水溶液為較佳。從 未曝光部之顯影溶解性的觀點來看，鹼顯影液中的鹼性物質之含量係以0.02質量%以上為較佳。另一方面，從更提升曝光部之圖案加工性的觀點來看，係以2.0質量%以下為較佳。為了提高顯影之均勻性，顯影液係以含有界面活性劑為較佳。由於顯影速度因顯影液之溫度而變化，因此顯影液溫度係以在18~40℃之範圍適當選擇為較佳。 As an image development process, image development with an alkali developing solution is preferable. As an alkaline developing solution, an organic alkaline developing solution, an inorganic alkaline developing solution, etc. are mentioned. As the inorganic alkaline developer, aqueous solutions of sodium carbonate, sodium hydroxide, and potassium hydroxide are preferred. As the organic base developer, tetramethylammonium hydroxide aqueous solution, methanol amine and other amine-based aqueous solutions are preferred. From the viewpoint of the development solubility of the unexposed portion, the content of the alkaline substance in the alkaline developing solution is preferably 0.02% by mass or more. On the other hand, it is preferably 2.0% by mass or less from the viewpoint of further improving the pattern processability of the exposed portion. In order to improve the uniformity of development, it is better for the developing solution to contain a surfactant. Since the developing speed varies with the temperature of the developing solution, it is better to select the temperature of the developing solution in the range of 18~40°C.

作為顯影方法，例如可列舉：浸漬顯影、淋浴顯影、攪拌器顯影等。係以適當選擇顯影液之溫度、流量及淋浴噴射壓力、顯影後的水洗溫度、流量及淋浴噴射壓力條件為較佳。為了去除基板上的殘渣，係以利用高壓來噴射顯影液或水洗水為較佳，噴出壓力係以0.01MPa~20MPa為較佳。 As an image development method, dip image development, shower image development, agitator image development etc. are mentioned, for example. It is better to properly select the temperature, flow rate and shower spray pressure of the developer, and the washing temperature, flow rate and shower spray pressure after developing. In order to remove residues on the substrate, it is better to use high pressure to spray developer or washing water, and the spray pressure is preferably 0.01MPa~20MPa.

作為顯影後的塗布膜圖案之加熱處理裝置，可列舉：熱風烘箱、加熱板等。加熱溫度係以180~300℃為較佳，加熱時間係以5~90分鐘為較佳。 As a heat processing apparatus of the coating film pattern after image development, a hot-air oven, a hot plate, etc. are mentioned. The heating temperature is preferably 180~300°C, and the heating time is preferably 5~90 minutes.

其次，舉例說明具有本發明之光間隔物的濾光片基板與液晶顯示裝置。 Next, an optical filter substrate and a liquid crystal display device having the photo-spacer of the present invention will be described with examples.

在一種態樣中，濾光片基板係在基板上具有本發明之光間隔物及畫素。可因應需要而具有黑矩陣、平坦化膜、透明電極、配向膜等。此外，本發明之光間隔物亦可形成於TFT陣列基板之側。 In one aspect, the optical filter substrate has the photo spacers and pixels of the present invention on the substrate. Black matrix, planarization film, transparent electrode, alignment film, etc. can be provided as needed. In addition, the photo spacers of the present invention can also be formed on the side of the TFT array substrate.

作為基板，可列舉：作為形成光間隔物之基板所例示者。 As a board|substrate, what was illustrated as a board|substrate on which a photo-spacer is formed is mentioned.

作為畫素，例如可列舉：紅色畫素、綠色畫 素、藍色畫素等。畫素可含有著色劑、樹脂、聚合性化合物、光聚合起始劑、其他添加劑等，可由包含此等之1種以上的組成物之硬化物所形成。作為著色劑，例如可列舉：有機顏料、無機顏料、染料。作為樹脂、聚合性化合物、光聚合起始劑、其他添加劑，例如可列舉：作為本發明之透明感光性樹脂組成物之成分所例示者。 Examples of pixels include red pixels, green pixels, and blue pixels. A pixel may contain colorants, resins, polymerizable compounds, photopolymerization initiators, other additives, etc., and may be formed from a cured product containing one or more of these components. As a coloring agent, an organic pigment, an inorganic pigment, and a dye are mentioned, for example. As a resin, a polymeric compound, a photoinitiator, and other additives, what was illustrated as a component of the transparent photosensitive resin composition of this invention is mentioned, for example.

作為畫素之形狀，例如可列舉：矩形、條紋、正方形、多角形、波形等。從增加開口部面積以提升穿透率的觀點來看，畫素寬度係以1μm以上為較佳。另一方面，從顯示更緻密的影像的觀點來看，畫素寬度係以100μm以下為較佳。畫素之膜厚係以1~5μm左右為較佳。 Examples of the shape of the pixel include rectangle, stripe, square, polygon, and wave. From the viewpoint of increasing the area of the opening to increase the transmittance, the pixel width is preferably greater than 1 μm. On the other hand, from the viewpoint of displaying a denser image, the pixel width is preferably 100 μm or less. The film thickness of the pixel is preferably about 1-5 μm.

係以在鄰接畫素間具有黑矩陣(以下為「BM」)為較佳。BM具有藉由對畫素間進行遮光，而提升顯示影像之對比的作用。BM可為藉由重疊彼此鄰接的畫素之一部分而形成之色重疊BM，而為了抑制畫素之高低差以更提升顯示影像，得到高遮光性，係以含有樹脂及遮光材為較佳。作為樹脂，係以聚醯亞胺系樹脂或丙烯酸系樹脂為較佳。作為遮光劑，例如可列舉：鈦黑、氮化鈦、碳化鈦、碳黑等。再者，可含有密合改良劑、高分子分散劑、聚合起始劑、酸產生劑、鹼產生劑、界面活性劑等。 It is better to have a black matrix (hereinafter referred to as "BM") between adjacent pixels. BM has the function of improving the contrast of the displayed image by shading the pixels. The BM can be a color overlapping BM formed by overlapping a part of adjacent pixels, and it is preferable to contain a resin and a light-shielding material in order to suppress the height difference of the pixels to further improve the display image and obtain high light-shielding properties. As the resin, polyimide resin or acrylic resin is preferred. As a light-shielding agent, titanium black, titanium nitride, titanium carbide, carbon black etc. are mentioned, for example. In addition, an adhesion improving agent, a polymer dispersant, a polymerization initiator, an acid generator, a base generator, a surfactant, and the like may be contained.

從提升遮光性與電阻值的觀點來看，BM之膜厚係以0.5μm以上為較佳，0.8μm以上為更佳。另一方面，從提升平坦性的觀點來看，BM之膜厚係以2.5μm 以下為較佳，2.0μm以下為更佳。 From the point of view of improving the light-shielding property and resistance value, the film thickness of BM is preferably 0.5 μm or more, more preferably 0.8 μm or more. On the other hand, from the viewpoint of improving flatness, the film thickness of BM is preferably 2.5 μm or less, more preferably 2.0 μm or less.

當具有畫素、BM之濾光片基板具有高低差時，係以具有平坦化膜為較佳。平坦化膜可形成於畫素、BM上之全面，亦可選擇性地形成於欲平坦化之部分。當平坦化膜形成於畫素、BM上之全面時，平坦化膜係以包含熱硬化性樹脂組成物之硬化物為較佳，當平坦化膜係選擇性地形成時，平坦化膜係以包含感光性樹脂組成物之硬化物為較佳。 When the filter substrate with pixels and BM has height difference, it is better to have a planarization film. The planarization film can be formed on the entire surface of the pixel and BM, and can also be selectively formed on the part to be planarized. When the planarization film is formed on the entire surface of the pixel or BM, the planarization film is preferably a cured product containing a thermosetting resin composition. When the planarization film is selectively formed, the planarization film is preferably a cured product containing a photosensitive resin composition.

平坦化膜係以含有樹脂為較佳，再者，可含有密合改良劑、高分子分散劑、聚合起始劑、酸產生劑、鹼產生劑、界面活性劑等。 The planarizing film preferably contains a resin, and may contain an adhesion improver, a polymer dispersant, a polymerization initiator, an acid generator, a base generator, a surfactant, and the like.

從平坦性與抑制由畫素溶出雜質的觀點來看，平坦化膜之膜厚係以0.5μm以上為較佳，1.0μm以上為更佳。另一方面，從提升透明性的觀點來看，平坦化膜之膜厚係以3.0μm以下為較佳，2.0μm以下為更佳。 From the viewpoint of planarity and suppression of elution of impurities from pixels, the film thickness of the planarizing film is preferably 0.5 μm or more, more preferably 1.0 μm or more. On the other hand, from the viewpoint of improving transparency, the film thickness of the planarizing film is preferably 3.0 μm or less, more preferably 2.0 μm or less.

本發明之濾光片基板可藉由在基板上形成本發明之光間隔物及畫素、因應需要的黑矩陣、平坦化膜等而得。作為畫素、黑矩陣、平坦化膜之形成方法，例如可列舉：光蝕刻法、印刷法、電鍍法等。 The optical filter substrate of the present invention can be obtained by forming the photo spacers and pixels of the present invention, black matrix and planarization film according to the needs on the substrate. As a method for forming a pixel, a black matrix, and a planarizing film, for example, a photoetching method, a printing method, a plating method, and the like are mentioned.

本發明之液晶顯示裝置具備：對向配置之濾光片基板與驅動元件側基板、配置於前述濾光片基板及該驅動元件側基板之間的使用本發明之樹脂組成物所形成之光間隔物、及填充於兩基板之間的液晶化合物。濾光片基板及驅動元件側基板通常具有：用來控制液晶之配向方向的液晶配向膜。例如當使用具有黑矩陣之濾光 片基板時，係以在非顯示區域(即黑矩陣)之上方具有光間隔物為較佳。此外，可在驅動元件側基板具有光間隔物，此時，亦以在驅動元件側基板上的非顯示區域之上方具有光間隔物為較佳。由於光間隔物係以使對向的2片基板間具有均勻間隔，並保持該間隔為目的所設置，因此可毫無差異地製作如玻璃般的硬質基板、如薄膜般的軟質基板。亦可使用於如液晶顯示裝置、電潤濕裝置般的用途。作為液晶配向膜，係以聚醯亞胺等樹脂膜為較佳。 The liquid crystal display device of the present invention comprises: an optical filter substrate and a driving element side substrate disposed opposite to each other, an optical spacer formed using the resin composition of the present invention disposed between the aforementioned optical filter substrate and the driving element side substrate, and a liquid crystal compound filled between the two substrates. The filter substrate and the driving element side substrate usually have a liquid crystal alignment film used to control the alignment direction of the liquid crystal. For example, when using a filter substrate with a black matrix, it is better to have a photo spacer above the non-display area (i.e. the black matrix). In addition, a photo spacer may be provided on the driving element side substrate, and in this case, it is also preferable to have a photo spacer above the non-display region on the driving element side substrate. Since the photo spacer is provided for the purpose of having a uniform space between two facing substrates and maintaining the space, it is possible to manufacture a hard substrate like glass and a soft substrate like a film without any difference. It can also be used in applications such as liquid crystal display devices and electrowetting devices. As the liquid crystal alignment film, resin films such as polyimide are preferred.

為了形成光間隔物所使用之感光性樹脂組成物，係均勻地塗布於基板上。塗布厚度係以0.5μm~500μm為較佳，從提高彈性恢復率的觀點來看，係以設為1μm以上為較佳，又，從塗布之均勻性的觀點來看，係以設為5μm以下為較佳。接著，以規定的圖案進行曝光‧顯影‧乾燥，因應需要而進行硬化處理，形成光間隔物。作為從基板上方觀察光間隔物之形狀時所觀察之形狀，係以條紋形狀、多角形、圓形為較佳。若為八角形以上的多角形、圓形，則尺寸之偏差變小而較佳，若為四角形則難以發生位置偏移而較佳。若製作正交於兩基板之條紋狀的光間隔物，則接觸面積難以受到偏差而較佳。作為剖面形狀，係以矩形、下底寬的梯形、上底寬的梯形、半球狀為較佳。為了使有效體積最大化，係以矩形為較佳，為了使配向膜難以損傷，係以半球狀為較佳。利用多段曝光、半透曝光而設置複數的高度亦較佳。同時設置主要支撐間隙之主間隔物、比主間隔物略 低的副間隔物亦可減少步驟數而較佳。同時設置平坦化膜亦進一步較佳。 The photosensitive resin composition used to form the photo-spacer is evenly coated on the substrate. The coating thickness is preferably 0.5 μm to 500 μm, more preferably 1 μm or more from the viewpoint of improving the elastic recovery rate, and more preferably 5 μm or less from the viewpoint of coating uniformity. Next, exposure, development, and drying are performed in a predetermined pattern, and curing treatment is performed as needed to form a photo-spacer. As the shape observed when the shape of the photo-spacer is observed from above the substrate, a stripe shape, a polygon, and a circle are preferable. If it is an octagonal or more polygonal shape or a circle, it is preferable that the variation in size is small, and if it is a square shape, it is preferable that the positional deviation hardly occurs. If the photo-spacers in the shape of stripes perpendicular to both substrates are produced, it is preferable that the contact area is less likely to be varied. As the cross-sectional shape, a rectangle, a trapezoid with a wide bottom, a trapezoid with a wide top, and a hemispherical shape are preferable. In order to maximize the effective volume, it is better to be rectangular, and to make the alignment film hard to damage, it is better to be hemispherical. It is also preferable to set multiple heights by using multi-segment exposure and semi-transparent exposure. At the same time, it is better to set the main spacer of the main support gap and the sub-spacer slightly lower than the main spacer to reduce the number of steps. It is also more preferable to provide a planarizing film at the same time.

其次，針對使用前述濾光片基板的液晶顯示裝置之製造方法之例進行說明。係以具有在濾光片基板及/或驅動元件側基板上藉由前述製造方法製造光間隔物之步驟為較佳。具體而言，係以使前述濾光片基板與驅動元件側基板對向，介隔光間隔物而貼合，從設置於密封部之注入口注入液晶後密封注入口，最後安裝IC驅動器等為較佳。當液晶顯示裝置具有液晶配向膜時，係以在塗布‧熱處理聚醯亞胺液後，藉由摩擦處理、紫外線處理而進行表面處理為較佳。從抑制細微的粉塵、靜電之產生，使液晶分子均勻且高精細地配向的觀點來看，係以藉由紫外線處理進行表面處理為較佳。 Next, an example of a method of manufacturing a liquid crystal display device using the aforementioned filter substrate will be described. It is preferable to have a step of manufacturing photo spacers on the optical filter substrate and/or the driving element side substrate by the aforementioned manufacturing method. Specifically, it is preferable to make the above-mentioned optical filter substrate and the driving element side substrate face each other, bond them through a photo spacer, inject liquid crystal from the injection port provided in the sealing part, seal the injection port, and finally mount the IC driver and the like. When the liquid crystal display device has a liquid crystal alignment film, it is preferable to perform surface treatment by rubbing treatment and ultraviolet treatment after coating and heat-treating the polyimide liquid. From the viewpoint of suppressing generation of fine dust and static electricity, and aligning liquid crystal molecules uniformly and with high precision, it is preferable to perform surface treatment by ultraviolet treatment.

[實施例] [Example]

以下列舉其實施例及比較例來詳細說明本發明，惟本發明並非限定於此等例子而解釋者。 The following examples and comparative examples are given to describe the present invention in detail, but the present invention is not limited to these examples and explained.

各物性及特性係藉由以下方法而測定、或進行評價。 Each physical property and characteristic was measured or evaluated by the following method.

(乙烯性不飽和基當量) (Ethylenically unsaturated group equivalent)

各成分之乙烯性不飽和基當量係藉由JIS K 0070：1992之試驗方法第6.0項所記載之方法，利用測定碘價而算出。此外，樹脂組成物之固體成分的乙烯性不飽和基當量，係由構成固體成分之各成分的質量比與該成分之乙烯性不飽和基當量而求出。 The ethylenically unsaturated group equivalent of each component was calculated by measuring the iodine value according to the method described in JIS K 0070: 1992 test method item 6.0. In addition, the ethylenically unsaturated group equivalent of the solid content of a resin composition is calculated|required from the mass ratio of each component which comprises a solid content, and the ethylenically unsaturated group equivalent of the said component.

(異氰酸酯基當量) (isocyanate group equivalent)

異氰酸酯基當量係藉由JIS K 1556：2006之試驗方法所記載之方法而求出。 The isocyanate group equivalent was determined by the method described in the test method of JIS K 1556:2006.

(胺基甲酸酯當量) (urethane equivalent)

關於將製造例1~10、12所得之異氰酸酯與羥基作為原料的聚合性化合物U-1~10與丙烯酸可溶性樹脂AC-2，係著眼於藉由紅外線光譜測定的屬於異氰酸酯之波峰的2260cm^-1之波峰，確認其強度成為0.000001以下。由於全部的異氰酸酯基轉化為胺基甲酸酯鍵結，因此從投入組成算出胺基甲酸酯當量。又，分子量之測定係除了已知的情形以外，藉由凝膠滲透層析圖以標準聚苯乙烯換算值求出。 With regard to the polymerizable compounds U-1 to 10 and the acrylic soluble resin AC-2 using the isocyanate and hydroxyl groups obtained in Production Examples 1 to 10 and 12 as raw materials, the intensity of the peak at 2260 cm ^-1 belonging to the isocyanate peak measured by infrared spectroscopy was confirmed to be 0.000001 or less. Since all the isocyanate groups were converted into urethane bonds, the urethane equivalent was calculated from the charged composition. In addition, the measurement of molecular weight was calculated|required by the standard polystyrene conversion value from the gel permeation chromatogram except the known case.

關於製造例11所得之鹼可溶性樹脂AC-1，係使用凝膠滲透層析，以標準聚苯乙烯換算值求出分子量，從原材料所包含之胺基甲酸酯鍵結的量算出。 The molecular weight of the alkali-soluble resin AC-1 obtained in Production Example 11 was obtained in terms of standard polystyrene using gel permeation chromatography, and calculated from the amount of urethane bonds contained in the raw material.

(酸價) (acid value)

藉由JIS K 0070：1992之試驗方法第3.1項之中和滴定法，測定酸價。 The acid value was measured by the neutralization titration method in Item 3.1 of the test method of JIS K 0070:1992.

製造例1(聚合性化合物U-1) Production Example 1 (polymerizable compound U-1)

在安裝了冷卻管、攪拌裝置及溫度計之反應容器，投入168.2質量份的六亞甲基二異氰酸酯異三聚氰酸體 及0.1質量份的二月桂酸二丁基錫，升溫至50℃後，耗費1小時滴入524.52質量份的二季戊四醇五丙烯酸酯後，在90℃下攪拌5小時而進行反應。測定該反應液中的殘存異氰酸酯量時，異氰酸酯量成為偵測極限以下，得到進行了胺基甲酸酯化反應之聚合性化合物(U-1)。U-1之分子量為2078.2，異氰酸酯當量為無限大(亦即未偵測出異氰酸酯基，無限大之意義係以下相同)，胺基甲酸酯當量為692.6g/mol，乙烯性不飽和基當量為138.5。1分子中的乙烯性不飽和基數為15。 In a reaction vessel equipped with a cooling tube, a stirring device, and a thermometer, 168.2 parts by mass of hexamethylene diisocyanate isocyanurate and 0.1 part by mass of dibutyltin dilaurate were put into the reaction vessel. After the temperature was raised to 50°C, 524.52 parts by mass of dipentaerythritol pentaacrylate was added dropwise over 1 hour, and the reaction was carried out by stirring at 90°C for 5 hours. When the amount of residual isocyanate in this reaction liquid was measured, the amount of isocyanate became below the detection limit, and the polymeric compound (U-1) which carried out the urethanization reaction was obtained. The molecular weight of U-1 is 2078.2, the isocyanate equivalent is infinite (that is, no isocyanate group is detected, the meaning of infinity is the same as below), the urethane equivalent is 692.6 g/mol, and the ethylenically unsaturated group equivalent is 138.5. The number of ethylenically unsaturated groups in one molecule is 15.

將以下所示之製造例1~10、製造例12之聚合性化合物的特性值示於表1。 Table 1 shows the characteristic values of the polymerizable compounds of Production Examples 1 to 10 and Production Example 12 shown below.

製造例2(聚合性化合物U-2) Production Example 2 (polymerizable compound U-2)

除了設為298.29質量份的季戊四醇三丙烯酸酯而取代製造例1之524.52質量份的二季戊四醇五丙烯酸酯以外，利用與製造例1同樣的方法，得到聚合性化合物 (U-2)。 A polymerizable compound (U-2) was obtained in the same manner as in Production Example 1 except that 298.29 parts by mass of pentaerythritol triacrylate was used instead of 524.52 parts by mass of dipentaerythritol pentaacrylate in Production Example 1.

製造例3(聚合性化合物U-3) Production Example 3 (polymerizable compound U-3)

除了設為750.75質量份的三季戊四醇七丙烯酸酯而取代製造例1之524.52質量份的二季戊四醇五丙烯酸酯以外，利用與製造例1同樣的方法，得到聚合性化合物(U-3)。 The polymeric compound (U-3) was obtained by the method similar to manufacture example 1 except having used 750.75 mass parts of tripentaerythritol heptaacrylates instead of 524.52 mass parts of dipentaerythritol pentaacrylates of manufacture example 1.

製造例4(聚合性化合物U-4) Production Example 4 (polymerizable compound U-4)

除了設為154.17質量份的六亞甲基二異氰酸酯脲二酮體而取代製造例1之168.2質量份的六亞甲基二異氰酸酯異三聚氰酸體，設為72.06質量份的丙烯酸而取代524.52質量份的二季戊四醇五丙烯酸酯以外，利用與製造例1同樣的方法，得到聚合性化合物(U-4)。 Except that 154.17 parts by mass of hexamethylene diisocyanate uretdione was used instead of 168.2 parts by mass of hexamethylene diisocyanate isocyanurate in Production Example 1, and 72.06 parts by mass of acrylic acid was used instead of 524.52 parts by mass of dipentaerythritol pentaacrylate, a polymerizable compound (U-4) was obtained in the same manner as in Production Example 1.

製造例5(聚合性化合物U-5) Production Example 5 (polymerizable compound U-5)

除了設為298.29質量份的季戊四醇四丙烯酸酯而取代製造例4之72.06質量份的丙烯酸以外，利用與製造例4同樣的方法，得到聚合性化合物(U-5)。 The polymeric compound (U-5) was obtained by the method similar to manufacture example 4 except having used 298.29 mass parts of pentaerythritol tetraacrylates instead of 72.06 mass parts of acrylic acid of manufacture example 4.

製造例6(聚合性化合物U-6) Production Example 6 (polymerizable compound U-6)

除了設為524.52質量份的二季戊四醇五丙烯酸酯而取代製造例4之72.06質量份的丙烯酸以外，利用與製造例4同樣的方法，得到聚合性化合物(U-6)。 The polymeric compound (U-6) was obtained by the method similar to manufacture example 4 except having used 524.52 mass parts of dipentaerythritol pentaacrylates instead of 72.06 mass parts of acrylic acid of manufacture example 4.

製造例7(聚合性化合物U-7) Production Example 7 (polymerizable compound U-7)

除了設為750.75質量份的三季戊四醇七丙烯酸酯而取代製造例4之72.06質量份的丙烯酸以外，利用與製造例6同樣的方法，得到聚合性化合物(U-7)。 The polymeric compound (U-7) was obtained by the method similar to manufacture example 6 except having used 750.75 mass parts of tripentaerythritol heptaacrylates instead of 72.06 mass parts of acrylic acid of manufacture example 4.

製造例8(聚合性化合物U-8) Production Example 8 (polymerizable compound U-8)

除了設為84.1質量份的六亞甲基二異氰酸酯而取代製造例4之154.17質量份的六亞甲基二異氰酸酯脲二酮體以外，利用與製造例4同樣的方法，得到聚合性化合物(U-8)。 A polymerizable compound (U-8) was obtained in the same manner as in Production Example 4 except that 84.1 parts by mass of hexamethylene diisocyanate was used instead of 154.17 parts by mass of hexamethylene diisocyanate uretdione in Production Example 4.

製造例9(聚合性化合物U-9) Production Example 9 (polymerizable compound U-9)

在安裝了冷卻管、攪拌裝置及溫度計之反應容器，投入168.2質量份的六亞甲基二異氰酸酯異三聚氰酸體及0.1質量份的二月桂酸二丁基錫，設為25℃後，耗費1小時滴入524.52質量份的二季戊四醇五丙烯酸酯後，在25℃下攪拌1天而進行反應，得到聚合性化合物群U-9。 168.2 parts by mass of hexamethylene diisocyanate isocyanurate and 0.1 part by mass of dibutyltin dilaurate were put into a reaction vessel equipped with a cooling pipe, a stirring device, and a thermometer. After setting the temperature at 25°C, 524.52 parts by mass of dipentaerythritol pentaacrylate was dropped in 1 hour, and then stirred at 25°C for 1 day to react to obtain polymerizable compound group U-9.

利用GPC對該U-9進行測定時，其為U-9-1、U-9-2、U-9-3之3種的混合物，分別取得並測定測定值時，存在異氰酸酯殘基，胺基甲酸酯反應未完成。U-9-1(構成比25%、分子量2078.2、異氰酸酯當量無限大、胺基甲酸酯當量692.7g/mol、乙烯性不飽和基當量138.55，1分子之乙烯性不飽和基數15)、U-9-2(構成比30%、分子量1553.63、異氰酸酯當量1553.6g/mol、胺 基甲酸酯當量776.8g/mol、乙烯性不飽和基當量155.36，1分子之乙烯性不飽和基數10)、U-9-3(構成比45%、分子量1029.11、異氰酸酯當量514.6g/mol、胺基甲酸酯當量1029.1g/mol、乙烯性不飽和基當量205.82，1分子之乙烯性不飽和基數5)之作為U-9全體的重量平均分子量、異氰酸酯當量、乙烯性不飽和基當量及胺基甲酸酯當量係如表1所示。 When this U-9 was measured by GPC, it was a mixture of three types of U-9-1, U-9-2, and U-9-3. When the measured values were obtained and measured respectively, there were isocyanate residues and the urethane reaction was not completed. U-9-1 (constituent ratio 25%, molecular weight 2078.2, isocyanate equivalent infinite, urethane equivalent 692.7g/mol, ethylenically unsaturated group equivalent 138.55, 1 molecule ethylenically unsaturated group 15), U-9-2 (constituent ratio 30%, molecular weight 1553.63, isocyanate equivalent 1553.6g/mol, urethane equivalent 776.8g/mol, Ethylenically unsaturated group equivalent 155.36, ethylenically unsaturated group number 1 molecule 10), U-9-3 (composition ratio 45%, molecular weight 1029.11, isocyanate equivalent 514.6g/mol, urethane equivalent 1029.1g/mol, ethylenically unsaturated group equivalent 205.82, 1 molecule ethylenically unsaturated group number 5) as the weight average molecular weight of U-9 as a whole, isocyanate equivalent, ethylenic unsaturated group The saturated group equivalent and urethane equivalent are shown in Table 1.

以下表示聚合性化合物U-1~U-9-3之結構式。 Structural formulas of polymerizable compounds U-1 to U-9-3 are shown below.

製造例10(聚合性化合物U-10) Production Example 10 (polymerizable compound U-10)

除了設為807質量份的二季戊四醇三丙烯酸酯‧環氧烷轉化物(日本化藥(股)製「KAYARAD」(註冊商 標)DPCA-20)而取代製造例1之524.52質量份的二季戊四醇五丙烯酸酯以外，利用與製造例1同樣的方法，得到聚合性化合物(U-10)。 Except that 524.52 parts by mass of dipentaerythritol pentaacrylate in Production Example 1 was replaced with 807 parts by mass of dipentaerythritol triacrylate‧alkylene oxide converted product ("KAYARAD" (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.), a polymerizable compound (U-10) was obtained in the same manner as in Production Example 1.

製造例11(鹼可溶性樹脂AC-1) Production Example 11 (Alkali-soluble resin AC-1)

將72g的甲基丙烯酸(MA)、40g的N-環己基馬來醯亞胺(CHMI)、30g的甲基丙烯酸甲酯(MMA)、3g的2,2’-偶氮雙(2-甲基丁腈)、0.5g的月桂基硫醇及220g的丙二醇單甲基醚(PGME)投入聚合容器中，在氮氣環境下在90℃下攪拌2小時後，將液溫升至100℃，再加熱攪拌5小時而使其反應。其次，使聚合容器內進行空氣取代，在所得之反應溶液添加97g的甲基丙烯酸環氧丙酯(GMA)、1.2g的二甲基苄基胺及0.2g的對甲氧基苯酚，在110℃下攪拌6小時後，追加PGME而得到固體成分濃度25.0質量%的鹼可溶性樹脂1(AC-1)之溶液。所得之AC-1的Mw為40,000，乙烯性不飽和基當量為350g/mol，酸價為85mgKOH/g。此外，在鹼可溶性樹脂AC-1中，MA構成通式(3)所示之結構單元，GMA賦予通式(4)所示之結構單元，CHMI賦予通式(5)所示之結構單元。 72g of methacrylic acid (MA), 40g of N-cyclohexylmaleimide (CHMI), 30g of methyl methacrylate (MMA), 3g of 2,2'-azobis(2-methylbutyronitrile), 0.5g of lauryl mercaptan and 220g of propylene glycol monomethyl ether (PGME) were put into a polymerization vessel, stirred at 90°C for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100°C, and then It was made to react by heating and stirring for 5 hours. Next, air was substituted in the polymerization container, 97 g of glycidyl methacrylate (GMA), 1.2 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained reaction solution, and after stirring at 110° C. for 6 hours, PGME was added to obtain a solution of alkali-soluble resin 1 (AC-1) with a solid content concentration of 25.0% by mass. The obtained AC-1 had a Mw of 40,000, an ethylenically unsaturated group equivalent of 350 g/mol, and an acid value of 85 mgKOH/g. In addition, in the alkali-soluble resin AC-1, MA constitutes the structural unit represented by the general formula (3), GMA confers the structural unit represented by the general formula (4), and CHMI confers the structural unit represented by the general formula (5).

製造例12(鹼可溶性樹脂AC-2) Production Example 12 (Alkali-soluble resin AC-2)

在內容量為2公升的5口反應容器內，添加686g的丙二醇單甲基醚乙酸酯(PGMAc)、332g的甲基丙烯酸環氧丙酯(GMA)、及6.6g的偶氮雙異丁腈(AIBN)，一邊吹 入氮氣一邊在80℃下加熱6小時，得到GMA之聚合物溶液。 686 g of propylene glycol monomethyl ether acetate (PGMAc), 332 g of glycidyl methacrylate (GMA), and 6.6 g of azobisisobutyronitrile (AIBN) were added to a 5-port reaction vessel with an internal capacity of 2 liters, and heated at 80° C. for 6 hours while blowing nitrogen gas to obtain a polymer solution of GMA.

其次，在所得之GMA之聚合物溶液添加168g的丙烯酸(AA)、0.05g的對甲氧苯酚(MQ)、0.5g的三苯基膦(TPP)，一邊吹入空氣一邊在100℃下加熱24小時，得到GMA樹脂之丙烯酸加成物溶液。 Next, 168 g of acrylic acid (AA), 0.05 g of p-methoxyphenol (MQ), and 0.5 g of triphenylphosphine (TPP) were added to the obtained GMA polymer solution, and heated at 100° C. for 24 hours while blowing in air to obtain an acrylic acid adduct solution of GMA resin.

再者，在所得之樹脂之丙烯酸加成物溶液添加186g的四氫鄰苯二甲酸酐，在7℃下加熱10小時。 Furthermore, 186 g of tetrahydrophthalic anhydrides were added to the obtained resin acrylic acid adduct solution, and it heated at 7 degreeC for 10 hours.

再添加117.22g的甲基丙烯醯氧乙基異氰酸酯(昭和電工製「Karenz MOI」)、117.22g的丙二醇單甲基醚乙酸酯(PGMAc)，一邊吹入空氣一邊在60℃下加熱12小時，追加PGME而得到固體成分濃度25.0質量%的鹼可溶性樹脂(AC-2)溶液。所得之AC-2之Mw為16,000，乙烯性不飽和基當量為260g/mol。胺基甲酸酯當量為1061.94g/mol。每1分子之乙烯性不飽和基之數為61.5，胺基甲酸酯當量為1061.9g/mol。 Furthermore, 117.22 g of methacryloxyethyl isocyanate (manufactured by Showa Denko "Karenz MOI") and 117.22 g of propylene glycol monomethyl ether acetate (PGMAc) were added, heated at 60° C. for 12 hours while blowing air in, and PGME was added to obtain an alkali-soluble resin (AC-2) solution with a solid content concentration of 25.0% by mass. The obtained AC-2 had a Mw of 16,000 and an ethylenically unsaturated group equivalent of 260 g/mol. The urethane equivalent weight was 1061.94 g/mol. The number of ethylenically unsaturated groups per molecule was 61.5, and the urethane equivalent was 1061.9 g/mol.

製造例13(光配向用配向膜之製作) Production example 13 (production of alignment film for photo-alignment)

在安裝了攪拌翼、氮氣導入管之500mL三口燒瓶，添加2.2636g的式(8)所示之化合物、104.0g的N-甲基-2-吡咯啶酮。使該溶液冰浴冷卻而將液溫設為5℃後，添加3.7364g的式(9)所示之化合物，在室溫下攪拌12小時。對其添加10.0g的γ-丁內酯及80.0g的丁基賽路蘇，在60℃下加熱攪拌溶液，得到溶質之重量平均分子量為16,000且樹脂分濃度為3質量%的光配向用配向膜用組 成物。 2.2636 g of the compound represented by the formula (8) and 104.0 g of N-methyl-2-pyrrolidone were added to a 500 mL three-necked flask equipped with a stirring blade and a nitrogen gas introduction tube. After cooling this solution in an ice bath to set the liquid temperature to 5° C., 3.7364 g of a compound represented by the formula (9) was added, and stirred at room temperature for 12 hours. 10.0 g of γ-butyrolactone and 80.0 g of butyl celuso were added thereto, and the solution was heated and stirred at 60° C. to obtain a composition for an alignment film for photoalignment with a weight average molecular weight of the solute of 16,000 and a resin concentration of 3% by mass.

製造例14(鹼可溶性樹脂AC-3) Production Example 14 (Alkali-soluble resin AC-3)

將95.3g的甲基丙烯酸(MA)、3.0g的2,2’-偶氮雙(2-甲基丁腈)、0.5g的月桂基硫醇及239g的3-甲氧基-1-丁醇溶液投入聚合容器中，在氮氣環境下在90℃下攪拌2小時後，將液溫升至100℃，再加熱攪拌5小時而使其反應。其次，使聚合容器內進行空氣取代，在所得之反應溶液添加143.7g的甲基丙烯酸環氧丙酯(GMA)、1.2g的二甲基苄基胺及0.2g的對甲氧基苯酚，在110℃下攪拌6小時後，追加3-甲氧基-1-丁醇而得到固體成分濃度40.0質量%的鹼可溶性樹脂3(AC-3)之溶液。所得之AC-3之Mw為10,000，乙烯性不飽和基當量為250g/mol)。 95.3 g of methacrylic acid (MA), 3.0 g of 2,2'-azobis(2-methylbutyronitrile), 0.5 g of lauryl mercaptan, and 239 g of 3-methoxy-1-butanol solution were put into a polymerization vessel, stirred at 90°C for 2 hours under a nitrogen atmosphere, then the liquid temperature was raised to 100°C, and heated and stirred for 5 hours to allow a reaction. Next, air was substituted in the polymerization container, 143.7 g of glycidyl methacrylate (GMA), 1.2 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the obtained reaction solution, and after stirring at 110° C. for 6 hours, 3-methoxy-1-butanol was added to obtain a solution of alkali-soluble resin 3 (AC-3) with a solid content concentration of 40.0% by mass. The obtained AC-3 had a Mw of 10,000 and an ethylenically unsaturated group equivalent of 250 g/mol).

(預焙膜之黏度) (viscosity of prebaked film)

除了使用無鹼玻璃基板(OA-10；日本電氣硝子(股)製；50mm×70mm、厚度0.7mm)作為塗布對象以外，使條件與各實施例所記載之條件相同而製作預焙膜。使用刮勺而將所得之預焙膜收集至90mm³以上，使用流變計(MCR-302；Anton Paar(股)製)與

15mm的平板，在測定厚度：0.5mm、頻率：1Hz、歪斜：0.5%之條件下，一邊以0.083℃/sec之升溫速度從20℃升溫至110℃，一邊測定在23℃下之黏度。 Except for using an alkali-free glass substrate (OA-10; manufactured by NEC Glass Co., Ltd.; 50 mm×70 mm, thickness 0.7 mm) as a coating object, a prebaked film was prepared under the same conditions as those described in each example. Use a spatula to collect the prebaked film obtained to more than 90 mm ³ , use a rheometer (MCR-302; manufactured by Anton Paar (Stock)) and

For a 15mm flat plate, under the conditions of measuring thickness: 0.5mm, frequency: 1Hz, and skew: 0.5%, the viscosity is measured at 23°C while increasing the temperature from 20°C to 110°C at a rate of 0.083°C/sec.

(光間隔物之彈性恢復率、彈性恢復率評價) (Elastic recovery rate and elastic recovery rate evaluation of photo-spacers)

在各實施例及比較例中形成之圓錐台狀的光間隔物，使用硬度計Fischer(Fischerscope H100；Helmut Fischer GmbH & Co公司製)與

50μm的平面型壓頭，製作以速度2.5mN/sec施加壓力直到到達負重50mN並保持5秒鐘後，以速度2.5mN/sec釋放而到達0mN後保持5秒鐘時之遲滯曲線。從所得之遲滯曲線，求出總變形量Ha[μm]、塑性變形量Hb[μm]，算出光間隔物之彈性恢復率(((Ha-Hb)/Ha)×100)(%)。算出針對5處所測定之數量平均值，作為彈性恢復率評價，藉由下述基準進行評價。將B判定以上作為合格。 The truncated conical photo-spacers formed in the respective Examples and Comparative Examples were tested using a hardness tester Fischer (Fischerscope H100; manufactured by Helmut Fischer GmbH & Co.) and

For a 50μm planar indenter, a hysteresis curve is produced when the pressure is applied at a speed of 2.5mN/sec until reaching a load of 50mN and held for 5 seconds, then released at a speed of 2.5mN/sec to reach 0mN and held for 5 seconds. From the hysteresis curve obtained, the total deformation Ha [μm] and the plastic deformation Hb [μm] were obtained, and the elastic recovery rate (((Ha-Hb)/Ha)×100)(%) of the photo-spacer was calculated. The numerical average value measured about 5 places was computed, and it evaluated by the following reference|standard as elastic recovery rate evaluation. A judgment of B or more was regarded as a pass.

E：彈性恢復率小於50% E: The elastic recovery rate is less than 50%

D：彈性恢復率為50%以上小於55% D: The elastic recovery rate is more than 50% and less than 55%

C：彈性恢復率為55%以上小於60% C: The elastic recovery rate is more than 55% and less than 60%

B：彈性恢復率為60%以上小於65% B: The elastic recovery rate is more than 60% and less than 65%

A：彈性恢復率為65%以上小於70% A: The elastic recovery rate is more than 65% and less than 70%

AA：彈性恢復率為70%以上小於75% AA: The elastic recovery rate is more than 70% and less than 75%

AAA：彈性恢復率為75%以上。 AAA: The elastic recovery rate is above 75%.

(光間隔物之耐滑動次數) (Sliding times of photo spacers)

將液晶面板固定在以每秒2cm進行往返運動之台座，使用施加了負重240g的以曲率半徑5mm之不鏽鋼球按壓的滑動試驗機，製作自500次起每隔500次試驗一次直到15000次之面板。將該面板解體而觀察對向的配向膜，繼續利用滑動試驗機之操作直到確認到損傷，將未觀測到損傷之最高次數作為耐滑動次數。又，作為滑動性評價，利用以下基準進行評價。將B判定以上作為合格。 The liquid crystal panel is fixed on a pedestal that reciprocates at 2cm per second, and a slide tester with a load of 240g applied to it is pressed by a stainless steel ball with a radius of curvature of 5mm, and the panel is tested every 500 times from 500 times until 15,000 times. The panel was disassembled to observe the facing alignment film, and the operation of the sliding tester was continued until damage was confirmed, and the highest number of times when no damage was observed was taken as the number of times of resistance to sliding. Moreover, as sliding property evaluation, it evaluated by the following reference|standard. A judgment of B or more was regarded as a pass.

E：耐滑動次數為500次以下 E: The sliding resistance is less than 500 times

D：耐滑動次數大於500次小於2000次 D: The number of sliding resistance is more than 500 times and less than 2000 times

C：耐滑動次數大於2000次小於3000次 C: The number of sliding resistance is greater than 2000 times and less than 3000 times

B：耐滑動次數大於3000次小於6000次 B: The number of sliding resistance is greater than 3000 times and less than 6000 times

A：耐滑動次數大於6000次小於10000次 A: The number of sliding resistance is greater than 6000 times and less than 10000 times

AA：耐滑動次數大於10000次小於15000次 AA: The number of sliding resistance is greater than 10,000 times and less than 15,000 times

AAA：耐滑動次數為15000次以上。 AAA: The sliding resistance is more than 15,000 times.

(黏度安定性評價) (Viscosity stability evaluation)

利用E型黏度計測定樹脂組成物之黏度，利用相對於製備首日而言在40℃下保管1週後之黏度的比而進行以下判定。將B判定以上作為合格。 The viscosity of the resin composition was measured with an E-type viscometer, and the following judgments were made using the ratio of the viscosity after storage at 40° C. for one week to the first day of preparation. A judgment of B or more was regarded as a pass.

E：黏度變化為±90%以上 E: Viscosity change is more than ±90%

D：黏度變化小於±90%且為±10%以上 D: The viscosity change is less than ±90% and more than ±10%

C：黏度變化小於±10%且為±3%以上 C: Viscosity change is less than ±10% and more than ±3%

B：黏度變化小於±3%且為±2%以上 B: The viscosity change is less than ±3% and more than ±2%

A：黏度變化小於±2%且為±1%以上 A: Viscosity change is less than ±2% and more than ±1%

AA：黏度變化小於±1%且為±0.1%以上 AA: The viscosity change is less than ±1% and more than ±0.1%

AAA：黏度變化小於±0.1%。 AAA: The viscosity change is less than ±0.1%.

(光間隔物之高度偏差) (height deviation of photo spacers)

在各實施例及比較例中形成之圓錐台狀的光間隔物之中，在基板面內20mm見方之範圍，在設置在對應於透鏡掃描曝光裝置所具備之多片透鏡與透鏡之接縫部分處，且正交於該多個透鏡排列為二列的方向之方向以一定的間隔選擇20個光間隔物，使用高低差測定器而測定高度之偏差(最大高度-最小高度)，藉由以下基準評價光間隔物之高度偏差。 Among the truncated conical photo-spacers formed in each of the examples and comparative examples, 20 photo-spacers were selected at regular intervals in a direction perpendicular to the direction in which the plurality of lenses are arranged in two rows, and the deviation in height (maximum height-minimum height) was measured using a height difference measuring device, and the height deviation of the photo-spacers was evaluated by the following criteria.

E：高度之偏差為0.060μm以上 E: The deviation of height is more than 0.060μm

D：高度之偏差為0.050μm以上小於0.060μm D: The height deviation is more than 0.050μm and less than 0.060μm

C：高度之偏差為0.040μm以上小於0.050μm C: The height deviation is more than 0.040μm and less than 0.050μm

B：高度之偏差為0.020μm以上小於0.040μm B: The height deviation is more than 0.020μm and less than 0.040μm

A：高度之偏差為0.010μm以上小於0.020μm A: The height deviation is more than 0.010μm and less than 0.020μm

AA：高度之偏差為0.005μm以上小於0.010μm AA: The height deviation is more than 0.005μm and less than 0.010μm

AAA：高度之偏差小於0.005μm。 AAA: The deviation of height is less than 0.005μm.

(顯影寬容度之評價) (evaluation of development latitude)

利用在各實施例及比較例中將顯影時間自20秒起 每隔5秒增減一次直到100秒之濾光片基板之光間隔物，以既無顯影缺陷亦無殘渣的時間範圍進行評價。 In each example and comparative example, the photo spacer of the filter substrate whose development time was increased or decreased every 5 seconds from 20 seconds to 100 seconds was used to evaluate the time range in which there were no development defects or residues.

E：無缺陷的顯影時間-無殘渣的顯影時間為10秒以下 E: Defect-free development time - The development time without residue is 10 seconds or less

D：無缺陷的顯影時間-無殘渣的顯影時間為15秒 D: Defect-free development time - 15 seconds for no-residue development

C：無缺陷的顯影時間-無殘渣的顯影時間為20秒 C: Defect-free development time - 20 seconds for no-residue development

B：無缺陷的顯影時間-無殘渣的顯影時間為25秒 B: Defect-free development time - 25 seconds for no-residue development

A：無缺陷的顯影時間-無殘渣的顯影時間為30秒 A: Defect-free development time - 30 seconds for no-residue development

AA：無缺陷的顯影時間-無殘渣的顯影時間為35秒 AA: Defect-free development time - 35 seconds for residue-free development

AAA：無缺陷的顯影時間-無殘渣的顯影時間為40秒以上。 AAA: Defect-free development time-the residue-free development time is 40 seconds or more.

(比較感光性樹脂組成物1(HK-1)之製備) (Comparative preparation of photosensitive resin composition 1 (HK-1))

在室溫下攪拌作為鹼可溶性樹脂溶液之AC-3(乙烯性不飽和基當量250g/mol、胺基甲酸酯當量無限大(亦即未偵測出胺基甲酸酯鍵結，無限大之意義係以下相同))：50.07質量份、作為聚合性化合物之二季戊四醇五丙烯酸酯與二季戊四醇六丙烯酸酯之混合物(「KAYARAD」(註冊商標)DPHA；日本化藥；以下為「DPHA」)(乙烯性不飽和基當量101.6、分子量559、胺基甲酸酯當量無限大)：8.58質量份、光聚合起始劑「ADEKA ARKLS」(註冊商標)N-1919；以下為「N1919」：0.18質量份(乙烯性不飽和基當量無限大(亦即未偵測出乙烯性不飽和基，無限大之意義係以下相同)、胺基甲酸 酯當量無限大)、「IRGACURE」(註冊商標)907(BASF Japan(股)製)；以下為「IC907」：0.27質量份(乙烯性不飽和基當量無限大、胺基甲酸酯當量無限大)、2,4-二乙基噻噸酮(「KAYACURE」(註冊商標)DETX-S；日本化藥(股)製；以下為「DETX」)：0.45質量份(乙烯性不飽和基當量無限大、胺基甲酸酯當量無限大)、界面活性劑「BYK」(註冊商標)-333(BYK-Chemie Japan(股)製)：以下「BYK-333」)0.11質量份(乙烯性不飽和基當量無限大、胺基甲酸酯當量無限大)、聚合抑制劑2,5-雙(1,1,3,3-四甲基丁基)氫醌(和光純藥工業(股)製；以下為「DOHQ」)：0.07質量份(乙烯性不飽和基當量無限大、胺基甲酸酯當量無限大)及40質量份的丙二醇單甲基醚(PMA)，得到比較感光性樹脂組成物(HK-1)。 AC-3 (ethylenically unsaturated group equivalent: 250 g/mol, urethane equivalent is infinite (that is, no urethane bond is detected, the meaning of infinity is the same below)) as an alkali-soluble resin solution was stirred at room temperature: 50.07 parts by mass, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA; Nippon Kayaku; hereinafter "DPHA") as a polymerizable compound (ethylene Unsaturated group equivalent weight 101.6, molecular weight 559, urethane equivalent weight is infinite): 8.58 parts by mass, photopolymerization initiator "ADEKA ARKLS" (registered trademark) N-1919; the following is "N1919": 0.18 parts by weight (ethylenically unsaturated group equivalent is infinite (that is, no ethylenically unsaturated group has been detected, the meaning of infinity is the same below), urethane equivalent is infinite), "IRGACU RE" (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.); the following is "IC907": 0.27 parts by mass (infinite ethylenically unsaturated group equivalent, infinite carbamate equivalent), 2,4-diethylthioxanthone ("KAYACURE" (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd.; hereinafter "DETX"): 0.45 parts by mass (infinite ethylenically unsaturated group equivalent, urethane Infinite equivalent), surfactant "BYK" (registered trademark)-333 (manufactured by BYK-Chemie Japan Co., Ltd.): 0.11 parts by mass of "BYK-333" below (infinite ethylenically unsaturated group equivalent, infinite urethane equivalent), polymerization inhibitor 2,5-bis(1,1,3,3-tetramethylbutyl)hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd.; hereinafter "DOHQ"): 0.0 7 parts by mass (the ethylenically unsaturated group equivalent is infinite and the urethane equivalent is infinite) and 40 parts by mass of propylene glycol monomethyl ether (PMA) to obtain a comparative photosensitive resin composition (HK-1).

該比較感光性樹脂組成物(HK-1)係在固體成分中包含66.77質量%的乙烯性不飽和基當量為250g/mol的鹼可溶性樹脂AC-3，在固體成分中包含28.61質量%的乙烯性不飽和基當量為101.6g/mol的聚合性化合物DPHA，該樹脂組成物之乙烯性不飽和基當量為182.3g/mol。 The comparative photosensitive resin composition (HK-1) contained 66.77% by mass of alkali-soluble resin AC-3 having an ethylenically unsaturated group equivalent of 250 g/mol in solid content, and 28.61% by mass of polymerizable compound DPHA having an ethylenically unsaturated group equivalent of 101.6 g/mol in solid content. The ethylenically unsaturated group equivalent of the resin composition was 182.3 g/mol.

(比較感光性樹脂組成物HK-2~HK-3、實施感光性樹脂組成物JK-1~JK-17之製作) (Comparison of photosensitive resin composition HK-2~HK-3, implementation of photosensitive resin composition JK-1~JK-17)

藉由與比較感光性樹脂組成物HK-1同樣的步驟順序，但質量摻合比如表2~表4所記載般製作。 It was produced by the same step sequence as the comparison photosensitive resin composition HK-1, but the mass blending ratio was recorded in Table 2~Table 4.

(比較例1) (comparative example 1)

(黑矩陣用樹脂組成物之製作) (Production of resin composition for black matrix)

混合150g的碳黑(三菱化學(股)製MA100)、75g的高分子分散劑(BYK-Chemie製「BYK」(註冊商標)6919、60質量%溶液)、100g的「CYCLOMER」(註冊商標)P(ACA)Z250(二丙二醇單甲基醚45質量%溶液、酸價110mgKOH/g、分子量20,000)、675g的丙二醇單甲基醚乙酸酯(PMA)而製作漿料。將放入漿料的燒杯以管路與DYNO-MILL相連，使用直徑0.5mm的二氧化鋯珠粒作為媒介，以圓周速度14m/s進行8小時的分散處理，製作黑矩陣用分散液(BMD-1)。 Mix 150 g of carbon black (MA100 manufactured by Mitsubishi Chemical Co., Ltd.), 75 g of polymer dispersant ("BYK" (registered trademark) 6919, 60% by mass solution manufactured by BYK-Chemie), 100 g of "CYCLOMER" (registered trademark) P(ACA) Z250 (dipropylene glycol monomethyl ether 45% by mass solution, acid value 110 mgKOH/g, molecular weight 20,000), 67 5 g of propylene glycol monomethyl ether acetate (PMA) was used to make the slurry. Connect the beaker containing the slurry to the DYNO-MILL with a pipeline, use zirconia beads with a diameter of 0.5mm as the medium, and carry out dispersion treatment at a peripheral speed of 14m/s for 8 hours to prepare a black matrix dispersion (BMD-1).

添加56.54g的BMD-1、3.14g的「CYCLOMER」P(ACA)Z250、2.64g的作為聚合性化合物之DPHA單體(日本化藥(股)製「KAYARAD」(註冊商標)DPHA)、0.330g的光聚合起始劑(ADEKA(股)製「ADEKA ARKLS」(註冊商標)NCI-831(以下為NCI-831))、0.04g的界面活性劑(BYK-Chemie製「BYK」(註冊商標)-333(以下為BYK-333))、0.01g的聚合抑制劑(DIC(股)製三級丁基兒茶酚(TBC))、37.30g的PMA，製作黑矩陣用的黑矩陣用樹脂組成物1(BM-1)。 Add 56.54 g of BMD-1, 3.14 g of "CYCLOMER" P(ACA) Z250, 2.64 g of DPHA monomer ("KAYARAD" (registered trademark) DPHA manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable compound, and 0.330 g of a photopolymerization initiator ("ADEKA ARKLS" (registered trademark) NCI-831 (hereinafter referred to as NCI-831) manufactured by ADEKA Co., Ltd.) )), 0.04g of a surfactant (“BYK” (registered trademark)-333 manufactured by BYK-Chemie (hereinafter referred to as BYK-333)), 0.01g of a polymerization inhibitor (tertiary butylcatechol (TBC) manufactured by DIC Co., Ltd.), 37.30g of PMA, black matrix resin composition 1 (BM-1) for producing a black matrix.

(紅色樹脂組成物之製作) (Production of red resin composition)

混合150g的C.I.Pigment Red 177(Ciba Specialty Chemicals(股)製「Cromophtal」Red(註冊商標)A2B)、75g 的「BYK」6919、100g的「CYCLOMER」P(ACA)Z250、675g的PMA而製作漿料。將放入漿料的燒杯以管路與DYNO-MILL相連，使用直徑0.5mm的二氧化鋯珠粒作為媒介，以圓周速度14m/s進行8小時的分散處理，製作紅用分散液(RD-1)。 A slurry was prepared by mixing 150 g of C.I. Pigment Red 177 ("Cromophtal" Red (registered trademark) A2B manufactured by Ciba Specialty Chemicals Co., Ltd.), 75 g of "BYK" 6919, 100 g of "CYCLOMER" P(ACA) Z250, and 675 g of PMA. Connect the beaker containing the slurry to the DYNO-MILL with a pipeline, and use zirconia beads with a diameter of 0.5mm as a medium to perform dispersion treatment at a peripheral speed of 14m/s for 8 hours to prepare a red dispersion (RD-1).

添加56.54g的RD-1、3.14g的「CYCLOMER」P(ACA)Z250、2.64g的DPHA單體、0.330g的光聚合起始劑(NCI-831)、0.04g的界面活性劑(BYK-333)、0.01g的聚合抑制劑(TBC)、37.30g的PMA，製作紅色樹脂組成物(R-1)。 Add 56.54g of RD-1, 3.14g of "CYCLOMER" P(ACA)Z250, 2.64g of DPHA monomer, 0.330g of photopolymerization initiator (NCI-831), 0.04g of surfactant (BYK-333), 0.01g of polymerization inhibitor (TBC), and 37.30g of PMA to prepare a red resin composition (R-1).

(藍色樹脂組成物之製作) (Production of blue resin composition)

混合150g的C.I.Pigment Blue 15：6(DIC(股)製EP193)、75g的「BYK」6919、100g的「CYCLOMER」P(ACA)Z250、675g的PMA而製作漿料。將放入漿料的燒杯以管路與DYNO-MILL相連，使用直徑0.5mm的二氧化鋯珠粒作為媒介，以圓周速度14m/s進行8小時的分散處理，製作藍用分散液(BD-1)。 150 g of C.I. Pigment Blue 15:6 (EP193 manufactured by DIC Co., Ltd.), 75 g of "BYK" 6919, 100 g of "CYCLOMER" P(ACA) Z250, and 675 g of PMA were mixed to prepare a slurry. Connect the beaker containing the slurry to DYNO-MILL with a pipeline, and use zirconia beads with a diameter of 0.5mm as a medium to carry out dispersion treatment at a peripheral speed of 14m/s for 8 hours to prepare a blue dispersion (BD-1).

添加29.02g的BD-1、12.70g的「CYCLOMER」P(ACA)Z250、4.68g的DPHA單體、0.585g的光聚合起始劑(NCI-930)、0.04g的界面活性劑(BYK-333)、0.01g的聚合抑制劑(TBC)、52.96g的PMA，製作藍色樹脂組成物(B-1)。 Add 29.02g of BD-1, 12.70g of "CYCLOMER" P(ACA)Z250, 4.68g of DPHA monomer, 0.585g of photopolymerization initiator (NCI-930), 0.04g of surfactant (BYK-333), 0.01g of polymerization inhibitor (TBC), and 52.96g of PMA to prepare a blue resin composition (B-1).

(著色材分散液之製作) (Production of coloring material dispersion)

混合105g的C.I.Pigment Green 59(FASTGEN Green C100)、C.I.Pigment Yellow 45(Clariant製「Hostaperm」Yellow HN4G)、75g的高分子分散劑(「BYK」6919)、100g的黏合劑樹脂(「ADEKA ARKLS」WR301)、675g的PMA而製作漿料。將放入漿料的燒杯以管路與DYNO-MILL相連，使用直徑0.5mm的二氧化鋯珠粒作為媒介，以圓周速度14m/s進行8小時的分散處理，製作Pigment Green 59分散液(D-1)。 Prepared by mixing 105g of C.I.Pigment Green 59 (FASTGEN Green C100), C.I.Pigment Yellow 45 ("Hostaperm" Yellow HN4G manufactured by Clariant), 75g of polymer dispersant ("BYK" 6919), 100g of binder resin ("ADEKA ARKLS" WR301), and 675g of PMA slurry. Connect the beaker containing the slurry to DYNO-MILL with a pipeline, use zirconia beads with a diameter of 0.5mm as the medium, and carry out dispersion treatment at a peripheral speed of 14m/s for 8 hours to prepare Pigment Green 59 dispersion (D-1).

添加47.361g的上述著色材分散液D-1、1.111g的WR301、1.863g的DPHA單體(日本化藥製「KAYARAD」(註冊商標)DPHA酸價0.1mgKOH/g)、0.192g的光聚合起始劑(ADEKA(股)製「ADEKA ARKLS」(註冊商標)NCI-831)、0.021g的鏈轉移劑(昭和電工(股)製「Karenz」(註冊商標)MT-PE1)、0.160g的密合改良劑(信越化學工業(股)製KBM-503)、0.040g的界面活性劑(BYK-Chemie製「BYK」(註冊商標)-333)、0.009g的聚合抑制劑(DIC製三級丁基兒茶酚(TBC))、7.243g的PMA、42.001g的二丙二醇單甲基醚乙酸酯(DPMA)而製作綠色樹脂組成物。 Add 47.361 g of the above-mentioned coloring material dispersion D-1, 1.111 g of WR301, 1.863 g of DPHA monomer (Nippon Kayaku "KAYARAD" (registered trademark) DPHA acid value 0.1 mgKOH/g), 0.192 g of photopolymerization initiator (ADEKA Co., Ltd. "ADEKA ARKLS" (registered trademark) NCI-831), 0.021 g of chain transfer agent ("Karenz" (registered trademark) MT-PE1 manufactured by Showa Denko Co., Ltd.), 0.160 g of adhesion improving agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 0.040 g of surfactant ("BYK" (registered trademark)-333 manufactured by BYK-Chemie), 0.009 g of polymerization inhibitor (tertiary butylcatechol (TBC) manufactured by DIC), 7.243 g of PMA, 42.001g of dipropylene glycol monomethyl ether acetate (DPMA) to make a green resin composition.

(濾光片基板之製作) (Manufacturing of filter substrates)

在無鹼玻璃上，以硬化後膜厚度成為1.5μm的方式塗布黑矩陣用樹脂BM-1，進行真空乾燥。介隔畫素節距50μm、黑矩陣寬度5μm寬的條紋狀光罩，以i線40mJ/cm²進行曝光，藉由0.3質量%四甲基銨水溶液進行50秒鐘 顯影，在230℃下進行30分鐘加熱硬化，形成黑矩陣。 On the non-alkali glass, resin BM-1 for black matrices was apply|coated so that the film thickness after hardening might become 1.5 micrometers, and it vacuum-dried. A striped mask with a pixel pitch of 50 μm and a black matrix width of 5 μm is exposed with an i-line of 40 mJ/cm ² , developed with a 0.3 mass % tetramethylammonium aqueous solution for 50 seconds, and heated and hardened at 230 ° C for 30 minutes to form a black matrix.

在其上以膜厚成為2.5μm的方式塗布紅色樹脂組成物R-1，進行真空乾燥。介隔50μm寬的條紋狀光罩，以i線40mJ/cm²進行曝光，藉由0.3質量%四甲基銨水溶液進行50秒鐘顯影，在230℃下進行30分鐘加熱硬化，形成畫素節距50μm的紅色畫素。 Red resin composition R-1 was applied thereon so that the film thickness became 2.5 μm, and vacuum-dried. Expose with i-line 40mJ/ ^cm2 through a striped mask with a width of 50μm, develop with 0.3 mass% tetramethylammonium aqueous solution for 50 seconds, heat and harden at 230°C for 30 minutes, and form red pixels with a pixel pitch of 50μm.

進一步在其上以膜厚成為2.5μm的方式塗布藍色樹脂組成物B-1，進行真空乾燥。介隔50μm寬的條紋狀光罩，以i線40mJ/cm²進行曝光，藉由0.3質量%四甲基銨水溶液進行50秒鐘顯影，在230℃下進行30分鐘加熱硬化，形成畫素節距50μm的藍色畫素。 Furthermore, the blue resin composition B-1 was applied so that the film thickness may become 2.5 micrometers, and it vacuum-dried. Expose with i-line 40mJ/ ^cm2 through a striped mask with a width of 50μm, develop with 0.3 mass% tetramethylammonium aqueous solution for 50 seconds, heat and harden at 230°C for 30 minutes, and form blue pixels with a pixel pitch of 50μm.

進一步在其上以硬化後膜厚成為2.5μm的方式塗布綠色樹脂組成物，在90℃下加熱乾燥10分鐘。介隔50μm寬的條紋形狀光罩，以i線100mJ/cm²進行曝光，藉由0.3質量%四甲基銨水溶液進行60秒鐘顯影，在230℃下進行30分鐘加熱硬化，形成畫素節距50μm的綠色畫素後，製作過塗(over coat)層。 Further, a green resin composition was applied thereon so that the film thickness after curing became 2.5 μm, and it was heated and dried at 90° C. for 10 minutes. Expose with i-line 100mJ/ ^cm2 through a stripe-shaped mask with a width of 50μm, develop with 0.3% by mass tetramethylammonium aqueous solution for 60 seconds, and heat and harden at 230°C for 30 minutes to form green pixels with a pixel pitch of 50μm, and then create an overcoat layer.

進一步在其上塗布比較感光性樹脂組成物1。在溫度：25℃、壓力：45Pa之條件下減壓乾燥200秒鐘後，在105℃下加熱乾燥(預焙)10分鐘後，冷卻至室溫，形成預焙膜。其次，作為透鏡掃描曝光裝置，利用FX-65S(Nikon(股)製)，介隔直徑7μm的圓形光罩，將包含i線：365nm、h線：405nm及g線：436nm的各波長之紫外線作為照射光，以60mJ/cm²之曝光量(i線換算)進行曝光。 Further, comparative photosensitive resin composition 1 was coated thereon. After drying under reduced pressure for 200 seconds under the conditions of temperature: 25°C and pressure: 45Pa, heat drying (prebaking) at 105°C for 10 minutes, and then cool to room temperature to form a prebaked film. Next, using FX-65S (manufactured by Nikon Co., Ltd.) as a lens scanning exposure device, through a circular mask with a diameter of 7 μm, ultraviolet light of each wavelength including i-line: 365 nm, h-line: 405 nm, and g-line: 436 nm was used as irradiation light, and exposure was performed at an exposure amount (i-line conversion) of 60 mJ/cm ² .

其次，將分別包含0.3質量%的TMAH、與0.3質量%的A-60之23℃的水溶液作為顯影液，進行60秒鐘淋浴顯影，進一步水洗並排水。最後，在230℃的烘箱內進行30分鐘加熱乾燥(後焙)，製作多片形成了上底6μm、下底9μm、高度3μm的光間隔物之濾光片基板。以數片進行彈性恢復率評價等之評價，其餘進入顯示裝置之製作步驟。 Next, a 23° C. aqueous solution containing 0.3 mass % of TMAH and 0.3 mass % of A-60 was used as a developer, and shower development was performed for 60 seconds, followed by further washing with water and draining. Finally, heating and drying (post-baking) was performed in an oven at 230° C. for 30 minutes to produce a plurality of optical filter substrates with photo-spacers of 6 μm on the bottom, 9 μm on the bottom, and 3 μm in height. Evaluations such as the evaluation of elastic recovery rate are carried out on several pieces, and the rest enter the production steps of display devices.

(顯示裝置之製作) (production of display device)

在無鹼玻璃上形成TFT元件、透明電極等，製作TFT陣列基板。在藉由前述方法所得之濾光片基板與陣列基板，在硬化後膜厚成為100nm的條件下塗布製造例12之光配向用配向膜用組成物，從相對於基板而言的垂直方向，介隔偏光板而照射紫外線之直線偏光，利用波長365nm以1.3J/cm²進行光偏向。在230℃下進行20分鐘燒製處理。 TFT elements, transparent electrodes, etc. are formed on alkali-free glass to make a TFT array substrate. The optical filter substrate and the array substrate obtained by the aforementioned method were coated with the alignment film composition for photo-alignment in Production Example 12 under the condition that the film thickness after curing was 100 nm, and the linearly polarized light of ultraviolet rays was irradiated through a polarizing plate from the vertical direction relative to the substrate, and the light was polarized at a wavelength of 365 nm at 1.3 J/cm ² . The firing treatment was performed at 230° C. for 20 minutes.

在陣列基板印刷摻合了微米棒之密封劑，貼合陣列基板與濾光片基板。從設置於密封部之注入口注入IPS液晶後，在液晶晶胞之兩面以偏光軸成為垂直的方式貼合偏光薄膜，得到液晶面板。在該液晶面板安裝背光光源，安裝TAB模組、印刷基板等，製作液晶顯示裝置。 Print the sealant mixed with microrods on the array substrate, and attach the array substrate and the filter substrate. After injecting IPS liquid crystal from the injection port provided in the sealing part, a polarizing film is bonded on both sides of the liquid crystal cell so that the polarization axis becomes vertical to obtain a liquid crystal panel. A backlight light source is mounted on the liquid crystal panel, and a TAB module, a printed circuit board, etc. are mounted to manufacture a liquid crystal display device.

該比較感光性樹脂組成物(HK-1)之乙烯性不飽和基當量為176.7，彈性恢復率為48.1且彈性恢復率評價為E。又，胺基甲酸酯僅包含IR測定極限以下，胺 基甲酸酯當量為實質無限大，採用測定下限值而作為1.0×10⁹進行計算。耐滑動次數為4000次，評價為B。 The comparative photosensitive resin composition (HK-1) had an ethylenically unsaturated group equivalent of 176.7, an elastic recovery rate of 48.1, and an elastic recovery rate evaluation of E. In addition, the urethane is included only below the IR measurement limit, and the urethane equivalent is substantially infinite, and the lower limit value of the measurement is adopted as 1.0×10 ⁹ for calculation. The number of times of sliding resistance was 4000 times, and the evaluation was B.

(比較例2~3、實施例1~17) (Comparative Examples 2~3, Examples 1~17)

除了將感光性樹脂組成物之組成變更為如表2~表4所示以外，與比較例1同樣地製作預焙膜、光間隔物及液晶顯示裝置。將評價樹脂組成物之質量%、乙烯性不飽和鍵結當量、胺基甲酸酯當量、胺基甲酸酯當量/乙烯性不飽和鍵結當量、彈性恢復率、彈性恢復率評價、耐滑動次數、滑動性評價之結果示於表5~表7。 Except having changed the composition of the photosensitive resin composition as shown in Table 2-Table 4, it carried out similarly to the comparative example 1, and produced the prebaked film, the photo-spacer, and the liquid crystal display device. Tables 5 to 7 show the results of evaluating the mass % of the resin composition, ethylenically unsaturated bond equivalent, urethane equivalent, urethane equivalent/ethylenically unsaturated bond equivalent, elastic recovery rate, evaluation of elastic recovery rate, number of times of sliding resistance, and sliding property evaluation.

(比較例1~3之比較) (Comparison of Comparative Examples 1~3)

相對於比較例1，改變摻合比、減少乙烯性不飽和鍵結當量之比較例2~3中，乙烯性不飽和基當量與彈性恢復率有相關性，可說為了將彈性恢復率設為合格的B判定以上，需要155g/mol以下。又，隨著彈性恢復率之提升，則耐滑動次數減少，此為權衡關係，可說僅憑乙烯性不飽和鍵結當量之增減無法兼顧。 Compared with Comparative Example 1, in Comparative Examples 2 to 3 in which the blending ratio was changed and the ethylenically unsaturated bond equivalent was reduced, the ethylenically unsaturated group equivalent has a correlation with the elastic recovery rate, and it can be said that in order to make the elastic recovery rate higher than the acceptable B judgment, it needs to be 155 g/mol or less. In addition, as the elastic recovery rate increases, the number of times of sliding resistance decreases. This is a trade-off relationship, and it can be said that only the increase or decrease of the ethylenically unsaturated bond equivalent cannot take care of both.

(實施例1與比較例3之比較) (Comparison between Example 1 and Comparative Example 3)

相對於比較例3而言，將DPHA之一部分取代為包含胺基甲酸酯鍵結之聚合性化合物U-1，將胺基甲酸酯當量調整為14523g/mol之實施例1，其恢復率評價維持AA而耐滑動次數從500次增加為3500次，滑動性評價從E提升為B。可說藉由包含胺基甲酸酯，而可兼顧恢復率評價與滑動性評價。在實施例2~16中亦可說藉由使用包含胺基甲酸酯鍵結之聚合性化合物或鹼可溶性樹脂，彈性恢復率評價維持AA而滑動性評價成為B判定以上。 Compared with Comparative Example 3, in Example 1, in which a part of DPHA was replaced by the polymerizable compound U-1 containing urethane linkages, and the urethane equivalent was adjusted to 14523 g/mol, the recovery rate evaluation maintained AA, while the number of sliding resistance increased from 500 to 3500, and the sliding evaluation increased from E to B. It can be said that by including urethane, evaluation of recovery rate and evaluation of slipperiness can be combined. In Examples 2 to 16, it can also be said that by using a polymerizable compound containing a urethane bond or an alkali-soluble resin, the elastic recovery rate evaluation maintained AA and the sliding property evaluation became B judgment or higher.

(實施例2~實施例5之比較) (Comparison of Embodiment 2 to Embodiment 5)

若試著觀察實施例2與胺基甲酸酯當量之值比其更小的實施例3~5，則可確認到胺基甲酸酯當量與耐滑動次數之相關性。可說只要胺基甲酸酯當量為50000g/mol以下，則可兼顧彈性恢復率評價。 When trying to observe Example 2 and Examples 3 to 5 in which the value of the urethane equivalent is smaller than this, the correlation between the urethane equivalent and the number of times of sliding resistance can be confirmed. It can be said that as long as the urethane equivalent is 50000 g/mol or less, the evaluation of the elastic recovery rate can be combined.

可說只要將胺基甲酸酯當量除以乙烯性不飽和基當量之值為10~200，則易於兼顧。 It can be said that as long as the value obtained by dividing the urethane equivalent by the ethylenically unsaturated group equivalent is 10 to 200, it is easy to balance.

(實施例7~14、17之比較) (Comparison of Embodiment 7～14,17)

當比較聚合性化合物不同的實施例7~14時，相對於1分子中的乙烯性不飽和基為2的實施例10而言，1分子中的乙烯性不飽和基為6個以上的實施例7~9、11~14之耐滑動次數多。又，在相同比較中，可說若包含胺基甲酸酯之聚合性化合物之分子量為700~3000，則耐滑動次數多，若為1000~3000，則耐滑動次數更多。 When comparing Examples 7 to 14 with different polymerizable compounds, Examples 7 to 9 and 11 to 14 with 6 or more ethylenically unsaturated groups in 1 molecule had more sliding resistance than Example 10 with 2 ethylenically unsaturated groups in 1 molecule. Also, in the same comparison, it can be said that if the molecular weight of the polymerizable compound containing urethane is 700-3000, the number of times of resistance to sliding is large, and if it is 1000-3000, the number of times of resistance to sliding is more.

(實施例7~9之比較) (Comparison of Embodiments 7 to 9)

在使用從具有通式(1)之結構的觀點來看為共通的聚合性化合物之實施例7~9中，1分子中的乙烯性不飽和基多者，其耐滑動次數變多。 In Examples 7 to 9 using common polymerizable compounds from the viewpoint of having the structure of the general formula (1), the number of ethylenically unsaturated groups in one molecule increased, and the number of times of resistance to sliding increased.

(實施例10~13之比較) (Comparison of Examples 10-13)

在使用從具有通式(2)之結構的觀點來看為共通的聚合性化合物之實施例10~13中，1分子中的乙烯性不飽和基多者，其耐滑動次數變多。 In Examples 10 to 13 using common polymerizable compounds from the viewpoint of having the structure of the general formula (2), the number of ethylenically unsaturated groups in one molecule increased, and the number of times of resistance to sliding increased.

(實施例7、12、14之比較) (Comparison of Embodiment 7, 12, 14)

使用了在通式(2)之結構使二季戊四醇五丙烯酸酯反應之U-6的實施例12，相較於使用了在六亞甲基異氰酸酯使二季戊四醇五丙烯酸酯反應之U-8的實施例14， 其耐滑動次數多。同樣地，使用了在通式(1)之結構使二季戊四醇五丙烯酸酯反應之U-1的實施例7，其耐滑動次數比實施例10更多。 In Example 12 using U-6 in which dipentaerythritol pentaacrylate was reacted with the structure of the general formula (2), the sliding resistance was higher than in Example 14 in which U-8 was used in which dipentaerythritol pentaacrylate was reacted with hexamethylene isocyanate. Similarly, Example 7 using U-1 in which dipentaerythritol pentaacrylate was reacted with the structure of the general formula (1) had a higher number of sliding resistance than Example 10.

(實施例9與實施例16之比較) (comparison of embodiment 9 and embodiment 16)

在聚合性化合物中包含環氧烷轉化物之實施例16係相較於實施例9，可在具有同等的彈性恢復率的同時，耐滑動次數從11000次大幅改善為18000次。 Compared with Example 9, Example 16, which contains an alkylene oxide conversion product in the polymeric compound, has the same elastic recovery rate, and the number of times of sliding resistance is greatly improved from 11,000 to 18,000.

(實施例18) (Example 18)

利用E型黏度計測定樹脂組成物JK-1之黏度，測定相對於製備首日而言在40℃下保管1週後之黏度的比並根據前述基準進行評價。黏度安定性為AAA而為特別優異者。 The viscosity of the resin composition JK-1 was measured with an E-type viscometer, and the ratio of the viscosity after storage at 40° C. for one week to the first day of preparation was measured and evaluated according to the aforementioned criteria. The viscosity stability is AAA and it is particularly excellent.

在樹脂組成物JK-1中形成之圓錐台狀圖案光間隔物之中，在相當於透鏡與透鏡之接縫部分的基板面內20mm見方之範圍，在正交於基板面內多個透鏡排列為二列的方向之方向以一定的間隔選擇20個光間隔物，使用高低差測定器而測定高度之偏差(最大高度-最小高度)，評價光間隔物之高度偏差。高度偏差為C。 Among the truncated conical pattern photo-spacers formed in the resin composition JK-1, 20 photo-spacers were selected at regular intervals in a direction perpendicular to the direction in which a plurality of lenses are arranged in two rows on the substrate surface within a range of 20 mm square in the substrate surface corresponding to the joint portion of the lens and the lens, and the height deviation (maximum height-minimum height) was measured using a height difference measuring device to evaluate the height deviation of the photo-spacers. The altitude deviation is C.

在使用樹脂組成物JK-1而製作之濾光片基板中，僅將光間隔物之顯影時間變更為自20起每隔5秒直到100秒而製作，利用無殘渣與缺陷的時間之長短評價顯影寬容度。顯影寬容度為AAA。 In the optical filter substrate manufactured using the resin composition JK-1, only the developing time of the photo-spacer was changed from 20 to 100 seconds every 5 seconds, and the developing latitude was evaluated by the length of time without residues and defects. The development latitude is AAA.

(實施例18~34) (Example 18~34)

除了將實施例之樹脂組成物JK-1分別取代為JK-2~JK-17以外，完全相同地實行實施例18~34。 Except that the resin composition JK-1 of the example was replaced by JK-2~JK-17, the examples 18~34 were carried out in the same manner.

將異氰酸酯當量、乾燥黏度、高度偏差評價、黏度安定性記載於表8~9。 The isocyanate equivalent, dry viscosity, height deviation evaluation, and viscosity stability are listed in Tables 8-9.

相對於實施例18而言，使用了包含通式(5)之結構的鹼可溶性樹脂之實施例19，可提升乾燥黏度，且高度偏差評價可隨之從C提升為B。 Compared with Example 18, Example 19 using the alkali-soluble resin having the structure of general formula (5) can increase the dry viscosity, and the height deviation evaluation can be improved from C to B accordingly.

(實施例19與實施例23之比較) (comparison of embodiment 19 and embodiment 23)

相對於實施例19而言，增加了包含通式(5)之結構的鹼可溶性樹脂之量的實施例23，其高度偏差評價可從B提升為AAA。 Compared with Example 19, Example 23, which increased the amount of the alkali-soluble resin containing the structure of general formula (5), could improve its height deviation evaluation from B to AAA.

(實施例18~31與32之比較) (Comparison of Embodiments 18-31 and 32)

可說若異氰酸酯當量為50000g/mol以上，則黏度安定性良好，且顯影寬容度良好。 It can be said that when the isocyanate equivalent is 50000 g/mol or more, the viscosity stability is good and the development latitude is good.

(實施例18~31與34之比較) (Comparison of Embodiments 18-31 and 34)

可說若胺基甲酸酯來自分子量3000以下的聚合性化合物，則顯影寬容度良好。 It can be said that when the urethane is derived from a polymerizable compound having a molecular weight of 3000 or less, the development latitude is good.

(樹脂組成物之分析) (Analysis of resin composition)

將如表4記載所摻合之5g的投入固體成分濃度30.0質量%的JK-16放入鋁製杯子(

45mm)，在130℃下加熱1小時而去除溶劑時，實測之固體成分濃度為30.0質量%。又，將利用四氫呋喃進行稀釋而調整為0.2質量%之樣品以GPC測定分子量，又，分別取得各成分。從面積比求出組成比。將各成分以1H-NMR鑑定結構，算出乙烯性不飽和基當量與胺基甲酸酯當量。根據使用之原材料的乙烯性不飽和基當量與胺基甲酸酯當量，算出作為樹脂組成物之乙烯性不飽和基當量與胺基甲酸酯當量時，確認到顯示非常高的一致性。 Put 5 g of JK-16 with a solid content concentration of 30.0 mass % blended as shown in Table 4 into an aluminum cup (

45 mm), and when the solvent was removed by heating at 130° C. for 1 hour, the measured solid content concentration was 30.0% by mass. Moreover, the molecular weight of the sample adjusted to 0.2 mass % diluted with tetrahydrofuran was measured by GPC, and each component was acquired separately. The composition ratio was obtained from the area ratio. The structure of each component was identified by 1H-NMR, and the ethylenically unsaturated group equivalent and the urethane equivalent were calculated. When the ethylenically unsaturated group equivalent and the urethane equivalent of the resin composition were calculated from the ethylenically unsaturated group equivalent and the urethane equivalent of the raw materials used, it was confirmed that a very high consistency was shown.

[產業上之可利用性] [Industrial availability]

本發明之感光性樹脂組成物可理想地使用作為用來形成液晶顯示裝置之光間隔物的材料。 The photosensitive resin composition of the present invention can be ideally used as a material for forming a photo-spacer of a liquid crystal display device.

Claims (12)

一種感光性樹脂組成物，其係含有鹼可溶性樹脂、光聚合起始劑及聚合性化合物之感光性樹脂組成物，其特徵為，其中在該樹脂組成物之固體成分中求出之胺基甲酸酯當量為1000~50000g/mol，且乙烯性不飽和基當量為100~155g/mol，作為該鹼可溶性樹脂，含有：具有A)下述通式(5)所示之結構單元、B)下述通式(6)所示之結構單元、與C)下述通式(7)所示之結構單元的樹脂；

(R¹⁵表示氫原子或甲基)；

(R¹⁶及R¹⁷分別獨立、且表示氫原子或甲基；X表示-CH₂CH(OH)CH₂O(C=O)-)；

(Y表示可具有取代基的骨架碳數為6~11之芳 基、可具有取代基的骨架碳數為7~10之芳烷基或可具有取代基的骨架碳數為3~10之環烷基)。 A photosensitive resin composition, which is a photosensitive resin composition containing an alkali-soluble resin, a photopolymerization initiator, and a polymerizable compound, wherein the urethane equivalent obtained in the solid content of the resin composition is 1,000 to 50,000 g/mol, and the ethylenically unsaturated group equivalent is 100 to 155 g/mol, and the alkali-soluble resin contains: A) a structural unit represented by the following general formula (5), B) the following general formula ( 6) the structural unit shown in, and C) the resin of the structural unit shown in the following general formula (7);

(R ¹⁵ represents a hydrogen atom or a methyl group);

(R ¹⁶ and R ¹⁷ are independent and represent a hydrogen atom or a methyl group; X represents -CH ₂ CH(OH)CH ₂ O(C=O)-);

(Y represents an aryl group with a skeleton carbon number of 6 to 11 which may have a substituent, an aralkyl group with a skeleton carbon number of 7 to 10 which may have a substituent, or a cycloalkyl group with a skeleton carbon number of 3 to 10 which may have a substituent). 如請求項1之感光性樹脂組成物，其中該聚合性化合物之至少一種成分在1分子中具有6個以上的乙烯性不飽和基。 The photosensitive resin composition according to claim 1, wherein at least one component of the polymerizable compound has 6 or more ethylenically unsaturated groups in one molecule. 如請求項1或2之感光性樹脂組成物，其中該聚合性化合物之至少一種成分在1分子中具有6個以上25個以下的乙烯性不飽和基。 The photosensitive resin composition according to claim 1 or 2, wherein at least one component of the polymerizable compound has 6 to 25 ethylenically unsaturated groups in one molecule. 如請求項1或2之感光性樹脂組成物，其中該聚合性化合物之分子量在700~3000之範圍內，且該聚合性化合物具有胺基甲酸酯鍵結。 The photosensitive resin composition according to claim 1 or 2, wherein the molecular weight of the polymeric compound is in the range of 700-3000, and the polymeric compound has a urethane bond. 如請求項1或2之感光性樹脂組成物，其中作為該聚合性化合物，包含下述通式(1)或下述通式(2)所示之聚合性化合物；

在此，通式(1)及(2)中，R¹~R³、R⁷~R⁸分別獨立表示可具有取代基的骨架碳數1~20之伸烷基、可具有取代基的骨架碳數1~20之環氧烷基、可具有取代基的骨架碳原子數7~30之伸芳基；R⁴~R⁶、R⁹~R¹⁰分別獨立表示通式(3)所示之一價的基；

在此，n為1~7之整數，R¹¹~R¹³分別表示下述通式(4)所示之一價的基；

在此，R¹⁴表示氫原子、或甲基。 The photosensitive resin composition according to claim 1 or 2, wherein the polymerizable compound includes a polymerizable compound represented by the following general formula (1) or the following general formula (2);

Here, in the general formulas (1) and (2), R ¹ ~ R ³ , R ⁷ ~ R ⁸ independently represent an alkylene group with a skeleton carbon number of 1 ~ 20 that may have a substituent, an epoxyalkylene group with a skeleton carbon number of 1 ~ 20 that may have a substituent, and an arylylene group with a skeleton carbon number of 7 ~ 30 that may have a substituent; R ⁴ ~ R ⁶ , R ⁹ ~ R ¹⁰ independently represent a valence group shown in the general formula (3);

Here, n is an integer of 1 to 7, and R ¹¹ to R ¹³ respectively represent a valence group shown in the following general formula (4);

Here, R ¹⁴ represents a hydrogen atom or a methyl group. 如請求項1或2之感光性樹脂組成物，其中在該聚合性化合物之固體成分中求出之異氰酸酯當量為50000g/mol以上。 The photosensitive resin composition according to claim 1 or 2, wherein the isocyanate equivalent obtained in the solid content of the polymerizable compound is 50000 g/mol or more. 如請求項1或2之感光性樹脂組成物，其中在該聚合性化合物之固體成分中求出之異氰酸酯當量為50000g/mol以上5000000g/mol以下。 The photosensitive resin composition according to claim 1 or 2, wherein the isocyanate equivalent obtained in the solid content of the polymerizable compound is not less than 50,000 g/mol and not more than 5,000,000 g/mol. 如請求項1或2之感光性樹脂組成物，其中將該胺基甲酸酯當量除以該乙烯性不飽和基當量之值為10~ 200。 Such as the photosensitive resin composition of claim 1 or 2, wherein the value of dividing the urethane equivalent by the ethylenically unsaturated group equivalent is 10~ 200. 如請求項1或2之感光性樹脂組成物，其中將該感光性樹脂組成物加熱處理後以厚度3μm塗布，在25℃、45Pa下減壓處理200秒鐘後，在105℃下加熱乾燥10分鐘所得之膜在23℃下之黏度為1×10³~1×10⁸Pa．s。 The photosensitive resin composition as claimed in claim 1 or 2, wherein the photosensitive resin composition is heat-treated and coated with a thickness of 3 μm, treated under reduced pressure at 25°C and 45Pa for 200 seconds, and then heated and dried at 105°C for 10 minutes. The viscosity of the film obtained at 23°C is 1×10 ³ ~1×10 ⁸ Pa. s. 一種光間隔物，其係使用如請求項1至9中任一項之感光性樹脂組成物而得。 A photo-spacer obtained by using the photosensitive resin composition according to any one of Claims 1-9. 一種液晶顯示裝置，其具有：對向配置之濾光片基板與驅動元件側基板、配置於該濾光片基板與驅動元件側基板之間的如請求項10之光間隔物、及封入該濾光片基板與驅動元件側基板間之液晶化合物。 A liquid crystal display device, which has: an optical filter substrate and a driving element side substrate disposed opposite to each other, an optical spacer according to claim 10 arranged between the optical filter substrate and the driving element side substrate, and a liquid crystal compound sealed between the optical filter substrate and the driving element side substrate. 如請求項11之液晶顯示裝置，其更具有光配向膜。 The liquid crystal display device according to claim 11, which further has a photo-alignment film.

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